Functionalization of polymers based on Koch chemistry and derivatives thereof

ABSTRACT

A Koch functionalized product which is the reaction product of at least one polymer having a number average molecular weight of at least 500 and at least one ethylenic double bond per polymer chain, with carbon monoxide and a nucleophilic trapping agent. The invention includes functionalized polymer, derivatives thereof and methods of making the same.

This is a continuation of application Ser. No. 07/992,403, filed Dec.17, 1992, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to an improved polymer and method tomake it, more particularly the invention relates to an polymer having atleast one carbon-carbon double bond reacted, according to the Kochreaction mechanism, with carbon monoxide in the presence of an acidiccatalyst to form a carbonyl or thiocarbonyl functional group, andderivatives thereof.

2. Description of Related Art

For the purpose of the present invention the term "polymer" is definedas a large molecule built up by the repetition of small, simple chemicalunits. (Billmeyer, J. R., Textbook of Polymer Sciences, 2nd Ed., J.Wiley p.3 (1971). Polymers are considered to be defined by averageproperties, and shall be considered to have a number average molecularweight of at least 500.

For the purpose of the present invention the term "hydrocarbon" refersto a compound comprising hydrogen and carbon which has specific orprecise properties (i.e., molecular weight) in contradistinction topolymeric materials which have average properties such as averagemolecular weight. However, the term "hydrocarbon" is not intended toexclude mixtures of different materials which individually arecharacterized by such specific and precise properties. Both hydrocarboncompounds as well as polymeric compounds have been reacted to formcarboxyl group containing compounds and their derivatives. Carboxylgroups have the general formula ##STR1## where R can be H, a hydrocarbylgroup or a substituted hydrocarbyl group.

The synthesis of carboxyl group containing compounds from olefinichydrocarbon compounds, carbon monoxide and water in the presence ofmetal carboxyls is disclosed in references such as N. Bahrmann, Chapter5, Koch Reactions, of the text "New Synthesis with Carbon Monoxide"edited by J. Falbe; Springer-Verlag, New York, N.Y. 1980. In accordancewith the disclosed Koch reactions, hydrocarbon compounds having olefinicdouble bonds are disclosed to react in two steps to form carboxylicacid-containing compounds. In the first step an olefin compound reactswith an acid catalyst and carbon monoxide in the absence of water. Thisis followed by a second step in which the intermediate formed during thefirst step undergoes hydrolysis or alcoholysis to form a carboxylic acidor ester. An advantage of the Koch reaction is that it can occur atmoderate temperatures of -20° C. to +80° C., and pressures up to 100bar.

Bahrmann et al. disclose a mechanism for a Koch reaction wherein anolefinic hydrocarbon compound is reacted with an acid catalyst andcarbon monoxide. A hydrogen compound having the formula:

    R(CH.sub.3)C═CH.sub.2

is reacted with an acid such as sulfuric acid and carbon monoxide.Initially, a carbenium ion forms having the formula:

    R(CH.sub.3).sub.2 C.sup.+

The carbenium ion reacts with carbon monoxide (CO) to form an acyliumcation having the formula:

    R(CH.sub.3).sub.2 C--CO.sup.+

The acylium cation can then be hydrolyzed with an alcohol or water toform an ester or an acid having the formula:

    R(CH.sub.3).sub.2 C--COOR'

where R is a hydrocarbon and R' is H or a hydrocarbon.

The Koch reaction can occur at double bonds where at least one carbon ofthe double bond is di-substituted to form a "neo" acid or ester (i.e.##STR2## Bahrmann et al. discloses isobutylene converted to isobutyricacid via a Koch-type reaction. The Koch reaction can also occur whenboth carbons are mono-substituted or one is monosubstituted and one isunsubstituted to form an "iso" acid (i.e. R₂ HC--COOR).

U.S. Pat. No. 2,831,877 discloses a multi-phase, acid catalyzed,two-step process for the carboxylation with carbon monoxide of olefinssuch as ethylene, propene, butene, isobutene or higher molecular weightolefins such as nonene, hexadecene and the like. This early referencepoints to considerations including yield and catalyst separation fromthe product. Disclosed catalysts include Broensted acids such as H₂ SO₄,HF, H₃ PO₄ as well as Broensted acids used in combination with Lewisacids. Useful Lewis acids include BF₃. It is disclosed that a system ofBF₃.H₂ O and methanol usually requires around 100 bar and temperaturesof 100° C. Milder conditions are reported with H₂ SO₄ and H₃ PO₄ (25/100bar CO pressure and 20°/100° C.). Very mild conditions are disclosedwith HF. Good yields are reported for methyl esters obtained in thepresence of BF₃.CH₃ OH. It is reported that depending on the weightratio of BF₃ to H₂ O the system can be homogeneous (ratio 1:1) orheterogeneous (ratio 1:2). The heterogeneous system has been reported toexhibit higher activity.

U.S. Pat. No. 2,967,873 to Koch et al. is directed to a process for theproduction of aliphatic and cycloaliphatic monocarboxylic acid alkylesters. The process entails the exposure of an olefin and carbon dioxideto the presence of a catalyst. The catalyst disclosed is a mixture of ahydroxy fluoroboric acid and an alkoxy fluoroboric acid. The backgroundof this patent discloses that catalysts including monohydroxyfluoroboric acid as well as the hydronium salt of this acid have beenused. The olefinic materials described include a variety of materialsincluding 2-methylpent-1-ene, diisobutene, isododecene, isopentadecene,and isononene prepared by polymerization of propene, olefins from thecleavage of oil products, and also dimers produced by the process of K.Ziegler. Alcohols useful in the method disclosed include methanol,ethanol and then propanol.

Complexes of mineral acids in water with BF₃ have been studied tocarboxylate olefins. U.S. Pat. No. 3,349,107 discloses processes whichuse less than a stoichiometric amount of acid as a catalyst. Examples ofsuch complexes are H₂ O.BF₃.H₂ O, H₃ PO₄.BF₃.H₂ O and HF.BF₃.H₂ O.

Sulfuric acid is known to be used as a catalyst in Koch reactions asdisclosed in Bahrmann, cited above. Bahrmann refers to Y. Komatsu etal., Maruzen Sekiyo Gihi 21, 51 (1976) regarding the use of 85% sulfuricacid as a catalyst for carboxylation of tertiary olefins in the presenceof trichloroethylene as a solvent. Chlorinated solvents are used toisolate the neo acid in the acid mixture. Other disclosures usingsulfuric acid include the use of mixtures of phosphoric and sulfuricacids as catalysts especially in the presence of copper salts, H.Kawasaki et al., J62164-645-A. The sulphonate which forms is disclosedto result in color, odor and acid quality problems and can be inhibitedby the disclosed procedure. The presence of substantial quantity ofphosphoric acid in the catalyst also induces phase separation in theproduct/catalyst recovery step.

Ya Eidus et al., Z. Org. Chem. 4 (3) 376 (1968) discloses the use ofphosphoric acid as a catalyst system which permits phase separation ofthe reaction products. However, the application of pure H₃ PO₄ comparedto H₂ SO₄ necessitates more severe reaction conditions (75/200 barinstead of 70/80 bar and 125°/150° C. instead of 10°/50° C.). Bahrmanndiscloses that H₃ PO₄ /BF₃ permits excellent separation of reactionproducts.

Hydrogen fluoride, HF, catalyst has been disclosed to be used in pureform as well as in an aqueous solution. Yields of greater than 95% havebeen obtained at high catalyst concentrations HF:olefin:H₂ O of 10:1:1.The low boiling point of hydrogen fluoride has been suggested to be anadvantage for catalyst separation via pressure distillation. Referencessuch as U.S. Pat. No. 3,527,779 suggest that acid strength of thecatalyst has a marked effect on the rate and selectivity of the Kochreaction. Examples of acid strength on the selectivity of pivalic acidare disclosed in the '779 patent. Strong acid catalysts promote theisomerization of linear unbranched olefins (carbon number greater thanor equal to 4) to form highly branched unsaturates. This is particularlyrelevant to the Koch reaction since by proper control of reactionconditions it is possible to carboxylate linear olefins to form isoacids. The use of more severe reaction conditions promotes isomerizationof the carbon backbone which, followed by carboxylation, results in theformation of neo acids.

Temperature and pressure are disclosed by Bahrmann to affect thereactants, intermediates and final products in the Koch reaction. Anincrease in reaction temperature generally has a favorable effect on neoacid yield. The magnitude of the temperature effect on selectivitydepends on the acid strength of the catalyst with the weaker thecatalyst the stronger the temperature effect. It is disclosed that theposition and rate of attainment of equilibrium of the followingreactions are determined by the temperature: dehydration/hydrationesterification/saponification (with alcoholic starting materials);isomerization of the carbenium ions; oligomerization/depolymerization ofcarbenium ions; and carboxylation/decarboxylation.

Bahrmann et al. disclose that, generally higher yields and more uniformproducts are achieved at high CO pressures. This is due to the trappingof the carbenium ion (via transformation into acyl complexes) whichsupresses the isomerization and oligomerization thereby preventing theformation of a series of by-products.

High levels of CO and sulfuric acid can be obtained by the addition ofanhydrous formic acid to the reaction median. Formic acid decomposes instrong acid at room temperature to form CO and water. The rate ofdecomposition of formic acid is acid strength dependent.

The amount of stirring can affect the yield of carboxylic acids in aKoch-type reaction mechanism using formic acid as a CO source. Lessstirring results in more secondary carbenium ions resulting iniso-carboxylic acids. It has also been reported that the conversion of1-hexene in the presence of BF₃.H₂ O resulted in increased neo acidcontent in the product increased on raising temperature from 20° C. to100° C. and on decreasing CO pressure from 85 to 27 bar (Gushcin, etal.; Neftekhimiya 12 (3) 383 (1972), Chem. Inf. 41 (1972) which wasreferred to in Bahrmann).

Other considerations reported by Bahrmann et al. which can determine theoutcome of a Koch reaction include the catalyst to olefin mole ratio,the product and catalyst recovery, and the reactor throughput andresidence time.

The use of a solvent can affect product/catalyst recovery. However,Onopchenko, A. et al., DE2811867 (Mar. 18, 1978) disclose that withhigher alpha olefins (greater than 16 carbons in length), higher yieldsof carboxylic acids were obtained in the absence of a solvent. Disclosedsolvents for use in Koch systems include saturated hydrocarbons such asn-heptane, cyclohexane, methylcyclohexane, isooctane, benzene,chlorobenzene, chloroform, trichloroethylene, tetrachloroethylene,methylene chloride, trifluoro and trichloro ethane, carbontetrachloride, fluorobenzene or mixtures thereof.

European Patent Publication No. 0,148,592 relates to the production ofcarboxylic acid esters and/or carboxylic acids by catalyzed reaction ofa polymeric hydrocarbon having carbon-carbon double bonds, carbonmonoxide and either water or an alcohol, optionally in the presence ofoxygen. The catalysts can be selected from metals such as palladium,rhodium, ruthenium, iridium, and cobalt in combination with a coppercompound. The reaction is conducted in the presence of a protonic acidwhich can include hydrochloric acid, sulfuric acid or an organic acidwhich can be a carboxylic acid. The reaction using transition metalcatalysts is described as an oxycarbonylation, (see, for example,Wender, I, Organic Synthesis via Metal Carbonyls, Volume 2). Usefulalcohols are disclosed in '592 to include R₂ CHOH, wherein R isindependently hydrogen, alkyl, aryl, or hydroxyalkyl or the two groups Rtogether form a ring. The carbon monoxide pressure may be theautogeneous pressure at the reaction temperature of 2 to 250 psig aboveautogeneous pressure. The reaction can be conducted in the presence orabsence of oxygen with oxygen preferred for improved yields. Optionally,and preferably, hydrocarbon solvents are used. The reaction is conductedat from 20° to 150° C. for 30 minutes to 8 hours. A preferred polymer isindicated to have at least 80% of its carbon-carbon double bonds in theform of terminal double bonds. Example polymers include butene polymers,ethylene copolymers and terpolymers, and vinyl aromatic dienecopolymers. The polymeric compound containing a carbon-carbon doublebond can be a hydrocarbon polymer containing greater than 20, forexample, greater than 30 carbon atoms. A disclosed polymer is butenepolymer, a preferred butene polymer is known as polyisobutylene,sometimes referred to as polyisobutene (PIB) which can be a low tomedium molecular weight liquid product obtained from polymerization ofat least partially purified isobutylene feeds. Examples of suitablepolyisobutylenes include liquid polyisobutylenes having a number averagemolecular weight in the range of from 200 to 2,500, preferably up to1,000.

U.S. Pat. No. 4,681,707 relates to a process for the production ofcarboxylic acid ester and/or a carboxylic acid which process comprisesreacting an unsaturated hydrocarbon with carbon monoxide and either analcohol or water in the presence of a protonic acid and a catalyst. Thecatalyst system and the alcohol are the same as disclosed in EP No.0,148,592 referred to above. The carboxylic acid is produced from anunsaturated compound containing 2 to 30 carbon atoms.

U.S. Pat. No. 4,902,822 discloses a process for the preparation ofcarboxylic acids or of esters thereof by contacting an olefinicunsaturated compound with carbon monoxide in the presence of water or analcohol, respectively, and of a catalytic system prepared by combining aruthenium compound and a compound having a non-coordinating ion of anacid with a pK_(a) below 0.5. The olefinic compounds are disclosed tohave from 2 to 30 carbon atoms. The non-coordinating anion is of an acidwhich can include sulfuric acid, sulfonic acid, or of an acid that canbe formed by interaction of a Lewis acid with a Broensted acid. Examplesof such Lewis acids include BF₃. The alcohols which are used aredisclosed to include aliphatic, cycloaliphatic or aromatic and may besubstituted with one or more substituents. The alcohol may include aphenol, including alkyl substituted phenol.

U.S. Pat. No. 4,927,892 relates to reacting a polymer or copolymer of aconjugated diene at least part of which is formed by 1,2 polymerizationwherein the α-carbon to the carboxyl group is unsubstituted with carbonmonoxide and water and/or alcohol in the presence of a catalyst preparedby combining a palladium compound, certain ligands and/or acid excepthydrohalogenic acids having a pk_(a) of less than 2. Useful Lewis acidsinclude BF₃.

U.S. Pat. No. 4,312,965 relates to a process of forming polymericpolyamines/amides by reacting an olefinic polymer derived from monomershaving multiple olefinic double bond, with carbon monoxide, water andammonia or amine in the presence of a rhodium catalyst.

The reaction at olefinic sites on hydrocarbons with carbon monoxide andwater has been addressed in U.S. Pat. No. 3,059,007. This referencerelates to improvements in the production of carboxylic acids frommonoolefins, carbon monoxide and water. The reaction is conducted at atemperature of -25° C. to 100° C., at a pressure of 20 to 150 atmospherein the presence of a highly acidic inorganic catalyst. The onlydisclosed catalyst was a mixture of H₃ PO₄, BF₃ and water in a molarratio of 1:1:1. The olefins are disclosed to have at least threecarbons. The acid formed is secondary or tertiary. Available unsaturatedcharge materials comprise unsaturated hydrocarbons, particularlymonoolefins such as propylene, butylene-1, butylene-2, isobutylene,branched or unbranched pentenes, hexenes, heptenes, octenes, nonenes,decanenes and high alkenes. Diisobutylene, propylene tetramer;cycloalkenes such as cyclopentenes and cyclohexenes are characterized asuseful polymers and copolymers.

U.S. Pat. No. 3,992,423 is directed to the production of carboxylicacids from olefins with a catalyst comprising a zeolite in an aluminumhydrosol. In particular, carboxylic acids are prepared by a processwhich comprises the treatment of an unsaturated hydrocarbon with acompound containing a hydroxy group and carbon monoxide in the presenceof the zeolite catalyst.

Puzitskii et al., Carbonylation of Olefins and Alcohols With CarbonMonoxide in the presence of a Catalyst System: BF₃.H₂ O-liquid SO₂, N.D. Zielinski, Institute of Organic Chemistry, Academy of Sciences of theU.S.S.R., Moscow, translated from Izvestiya Academii Nauk SSR, SeriyaKhimicheskaya, No. 10, pp. 2331-2334, October, 1977. Original articlesubmitted Jan. 4, 1977, published by the Plenum Publishing Company,1978. This article discloses that it was known that olefins, withbranching at the double bond, and tertiary alcohols in a mixture withmethanol or ethanol are selectively carbonylated to esters under mildconditions (-70° C., atmospheric pressure) in the presence of thecatalyst system SbCl₃ --HCl-liquid SO₂. The Puzitskii paper disclosesthat branched hydrocarbon olefins and tertiary alcohols are easilycarbonylated under mild conditions (-30° C., atmospheric pressure) inthe presence of the catalyst system BF₃.H₂ O-liquid SO₂. Liquid SO₂, asa solvent with a high dielectric constant facilitates the formation ofcarbenium and acylium ions from olefins or alcohols and CO. Liquid SO₂has been found to have an effect on CO by facilitating its polarizationand activity.

U.S. Pat. No. 4,262,138 discloses a process wherein ethylene orpropylene are carbonylated with carbon monoxide to form carboxylic acidesters in the presence of a catalyst complex of one mole of BF₃ and onemole of alcohol.

U.S. Pat. No. 4,256,913 discloses that propylene and ethylene may becarbonylated to form carboxylic acids or carboxylic esters in thepresence of a catalyst complex containing one mole of BF₃ and one moleof a second complexing component. In the case of the formation of theester, the second complexing component is an alcohol, while in the caseof the preparation of carboxylic acid, the second complexing componentis water. It is disclosed that isobutyric acid and propionic acid formedfrom propylene and ethylene, respectively, in the presence of BF₃.H₂ Ocatalyst may be dehydrogenated to prepare methacrylic acid and acrylicacid respectively.

U.S. Pat. No. 4,717,755 describes production of a propylene homopolymeror copolymer having a terminal carboxyl group by polymerizing withV(aceylacetonate)₃ and Al(C₂ H₅)₂ Cl and terminating the polymerizationwith carbon monoxide.

U.S. Pat. No. 4,704,427 teaches a method of modifying a rubber includingsubjecting the rubber to a carboxylation with, inter alia, carbonmonoxide in the presence of a metal carbonyl compound. ChemicalAbstracts '77 (12) 76298 likewise discloses a method of reacting arubber with carbon monoxide in the presence of a metal carbonyl compoundto introduce carboxyl groups into the rubber.

U.S. Pat. No. 4,980,422 teaches functionalizing a polymerized conjugateddiene by contacting it with carbon monoxide and an alcohol in thepresence of a catalyst comprising an amine ligand and a cobalt compound.The polymers formed having appended ester groups or terminal carboxylgroups when the o-carbon carboxyl group is unsubstituted.

U.S. Pat. No. 4,798,873 relates to carboxylic acid functionalizedpolyolefins prepared by olefin polymerization using organometalliccatalysts followed by carbonylation with CO₂.

Other disclosures of interest include U.S. Pat. Nos. 4,929,689;4,539,654; 3,910,963; 4,323,698; 4,224,232; 3,870,734; 4,717,755;4,518,798; 2,586,070 and Japanese Ref. 51-41320.

Polymers functionalized with carboxylic acid, ester and the like groups,are useful for a variety of purposes. For example, U.S. Pat. No.3,903,003 teaches the use of a terminally carboxylated, substantiallycompletely hydrogenated polyisoprene which is reacted with apolyalkylene amine or hydroxyl polyalkylene amine and formed into alubricating composition. There is particularly disclosed apolymerization of isoprene using a lithium based initiator. The polymerproduced is referred to as a living polymer with the end of the polymerchain associated with the lithium radical. The lithium polymer issubjected to carboxylation such as by reaction with carbon dioxide toform a polyisoprene having a terminal carboxyl group.

U.S. Pat. No. 4,857,217 teaches a dispersant additive which is an adductof (a) a polyolefin substituted with dicarboxylic acid producingmoieties and (b) an amidoamine or thioamidoamine. A functionalizedpolymer which was used in the foregoing dispersant and lubricantcompositions is an alkenyl succinic anhydride produced by reactingmaleic anhydride and polyisobutylene. The polymer to be substituted withthe dicarboxylic acid is described as a polyolefin polymer or copolymerwhich can be made by a variety of means and reacted with a C₄ to C₁₀unsaturated dicarboxylic acid, anhydride or ester. The olefin anddicarboxylic acid material can be reacted by simply heating together, asdisclosed in U.S. Pat. Nos. 3,361,673 and 3,401,118, to cause a thermal"ene" reaction to take place. Alternatively, the olefin polymer canfirst be halogenated, for example, chlorinated or brominated at atemperature of from 60° C. to 250° C. The halogenated polymer can thenbe reacted with sufficient unsaturated acid or anhydride so that theproduct obtained will contain the desired number of moles of unsaturatedacid per mole of halogenated polymer. There is no disclosure of reactingan unsaturated polymer in accordance with Koch-type chemistry toincorporate a carboxyl group.

SUMMARY OF THE INVENTION

The present invention relates to a polymer or copolymer functionalizedwith at least one carboxylic acid, carboxylic ester or thiol esterfunctional group. The functionalized polymer is derived from a polymercomprising at least one non-aromatic carbon-carbon double bond, alsoreferred to as an olefinically unsaturated bond, or an ethylenicallyunsaturated bond. The polymer is functionalized at the point of olefinunsaturation via a Koch reaction to form the carboxylic acid, carboxylicester or thiol ester.

Koch reactions are known in the art as presented by Bahrmann et al.referred to in the Background. However, this reaction has not heretoforebeen applied to polymers having number average molecular weights greaterthan 500 and preferably greater than 1,000. In accordance with thepresent invention, a Koch process comprises contacting a polymercomposition comprising at least one polymer having at least onecarbon-carbon double bond, with an acid catalyst and carbon monoxide inthe presence of water or alcohol. The catalyst is preferably a classicalBroensted acid or Lewis acid catalyst. These catalysts which are usefulfor Koch reactions, are distinguishable from transition metal catalystsof the type useful in hydroformylation as described above. The Kochreaction is conducted in a manner and under conditions sufficient toform a carbenium ion at the site of said carbon-carbon double bond. Thecarbenium ion is reacted with carbon monoxide to form an acylium cation,which in turn is reacted with at least one nucleophilic trapping agentselected from the group consisting of water or at least one hydroxyl orone thiol group containing compound. The Koch reaction as applied topolymers in accordance with the present invention has resulted in yieldsof functionalized polymer of at least 40, preferably at least 50, morepreferably at least 80, yet more preferably at least 90 mole % of thepolymer reacting to form acylium cations which form functional groups,e.g. carbonyl functional groups.

The composition of the present invention comprises functionalizedpolymer of the formula: ##STR3##

POLY represents polymer functionalized by the parenthetical substituentand having a number average molecular weight of at least about 500, andin specific embodiments the following number average molecular weightranges, at least about 2,500; at least about 2,800; at least about3,000; from 500 to 15,000,000; 500 to 20,000; 500 to 10,000; 1,000 to10,000; 1,500 to 5,000; 20,000 to 200,000; 20,000 to 100,000; 25,000 to80,000; and 25,000 to 60,000.

POLY- is derived from unsaturated polymer. Preferred unsaturatedpolymers include those selected from the group consisting of polyalkenesderived from monoolefinic monomers, diolefinic monomers and copolymersthereof.

The letter n is greater than 0 and represents the functionality (F) ofthe functionalized polymer wherein the functional group is representedby the formula: ##STR4## which functional group contains the acyl group##STR5## Specific embodiments of n include 1≧n>0; 2≧n>1; and n>2. n canbe determined by C¹³ NMR. The number of functional groups needed fordesired performance will typically increase with number averagemolecular weight of the polymer. In effect, there can be a controllednumber of functional groups per total molecular weight of polymer. Themaximum value of n will be determined by the number of double bonds perpolymer chain in the unfunctionalized polymer.

R¹ and R² can be the same or different and are selected from -H, ahydrocarbyl group and a polymeric group.

Y is selected from the group consisting of O, and S.

R³ is selected from H, hydrocarbyl, and a polymeric groups, wherein thehydrocarbyl group can include alkyl groups, hetero-substitutedhydrocarbyl groups, aromatic groups, substituted aromatic groups andhetero-substituted aromatic groups.

In specific and preferred embodiments the "leaving group" (--YR³) has apKa of less than or equal to 12, preferably less than 10, and morepreferably less than 8. The pKa is determined from the correspondingacidic species HY-R³ in water at room temperature.

Where the leaving group is a simple acid or alkyl ester, the system isvery stable especially when the % neo substitution increases. However,as will be described below, when the leaving groups are more stable,these compounds are more difficult to derivatize.

The present invention is especially useful to make "neo" functionalizedpolymer which are generally more stable and less labile than isostructures. By neo structure, it is meant that R¹ and R² are selectedsuch that at least 50 mole % of the ##STR6## groups of Formula I do nothave both R¹ and R² represented by hydrogen, but preferably a group suchas a hydrocarbyl group. In more specific embodiments the polymer can beat least 50, more specifically at least 60, yet more specifically atleast 80 mole percent neo. The polymer can be greater than 90, or 99 andeven about 100 mole percent neo.

In one preferred composition the polymer defined by formula (I), Y is O(oxygen), R¹ and R² can be the same or different and are selected fromH, a hydrocarbyl group, and a polymeric group.

In another preferred embodiment Y is O or S, R¹ and R² can be the sameor different and are selected from H, a hydrocarbyl group a substitutedhydrocarbyl group and a polymeric group, and R³ is selected from asubstituted hydrocarbyl group, an aromatic group and a substitutedaromatic group. This embodiment is generally more reactive towardsderivatization with amines and alcohol compounds especially where the R³substituent contains electron withdrawing species. It has been foundthat in this embodiment, a preferred leaving group, HYR³, has a pKa ofless than 12, preferably less than 10 and more preferably 8 or less. ThepKa of the leaving group determines how readily the system will reactwith derivatizing compounds to produce derivatized product.

In a particularly preferred composition, R³ is represented by theformula: ##STR7## wherein X, which may be the same or different, is anelectron withdrawing substituent, T, which may be the same or different,represents a non-electron withdrawing substituent (e.g. electrondonating), and m and p are from 0 to 5 with the sum of m and p beingfrom 0 to 5. More preferably, m is from 1 to 5 and preferably 1 to 3. Ina particularly preferred embodiment X is selected from a halogen,preferably F, C₁ and CF₃, cyano groups and nitro groups and p=0. Apreferred R³ is derived from 2,4-dichlorophenol.

The composition of the present invention includes derivatized polymerwhich is the reaction product of the Koch functionalized polymer and aderivatizing compound. Preferred derivatizing compounds includenucleophilic reactant compounds including amines, alcohols,amino-alcohols, metal reactant compounds and mixtures thereof.Derivatized polymer will typically contain at least one of the followinggroups: amide, imide, oxazoline, and ester, and metal salt. Theparticular end use of the derivatized polymer will control the polymerMn and functionality.

The Koch reaction permits controlled functionalization of unsaturatedpolymers. When a carbon of the carbon-carbon double bond is substitutedwith hydrogen, it will result in an "iso" functional group, i.e. one ofR¹ or R² of Formula I is H; or when a carbon of the double bond is fullysubstituted with hydrocarbyl groups it will result in a "neo" functionalgroup, i.e. both R¹ or R² of Formula I are non-hydrogen groups.

Polymers produced by processes which result in a terminally unsaturatedpolymer chain can be functionalized to a relatively high yield inaccordance with the process of the present invention. In particular, ithas been found that the neo acid functionalized polymer can bederivatized to a relatively high yield. This makes possible the use ofrelatively inexpensive materials i.e., carbon monoxide at relatively lowtemperatures and pressures. The leaving group --YR³ can be removed andrecycled upon derivatizing the Koch functionalized polymer with aminesor alcohols.

The present invention includes oleaginous compositions comprising theabove functionalized, and/or derivatized polymer. Such compositionsinclude lubricating oil compositions and concentrates.

The process of the present invention relates to a polymer having atleast one olefinic unsaturation reacted via a Koch mechanism to form thecarbonyl or thiol carbonyl group-containing compounds as well asderivatives thereof. The polymers react with carbon monoxide in thepresence of an acid catalyst or a catalyst complexed with a nucleophilictrapping agent. A preferred catalyst is BF₃ and preferred catalystcomplexes include BF₃.H₂ O and BF₃ complexed with 2,4-dichlorophenol.The starting polymer reacts with carbon monoxide at points ofunsaturation to form either iso- or neo- acyl groups with thenucleophilic trapping agent, e.g. water, alcohol (preferably asubstituted phenol) or thiol to form respectively a carboxylic acid,carboxylic ester group, or thio ester.

Without wishing to be bound by any particular theory, it is believedthat when at least one polymer having at least one carbon-carbon doublebond, is contacted with an acid catalyst or catalyst complex having aHammett Scale acidity value of less than -7, preferably from -8.0 to-11.5, a carbenium ion will form at the site of one of the carbon-carbondouble bonds. The carbenium ion then reacts with carbon monoxide to forman acylium cation. The acylium cation reacts with at least onenucleophilic trapping agent as defined herein. At least 40 mole %,preferably at least 50 mole %, more preferably at least 80 mole %, andmost preferably 90 mole % of the polymer double bonds will react to formacyl groups wherein the non-carboxyl portion of the acyl group isdetermined by the identity of the nucleophilic trapping agent, i.e.water forms acid, alcohol forms acid ester and thiol forms thio ester.

The polymer functionalized by the recited process of the presentinvention can be isolated using fluoride salts. The fluoride salt can beselected from the group consisting of ammonium fluoride, and sodiumfluoride.

Preferred nucleophilic trapping agents are selected from the groupconsisting of water, monohydric alcohols, polyhydric alcohols,hydroxyl-containing aromatic compounds and hetero substituted phenoliccompounds. The catalyst and nucleophilic trapping agent can be addedseparately or combined to form a catalytic complex.

The functionalized or derivatized polymers of the present invention areuseful as lubricant additives such as dispersants, viscosity improversand multifunctional viscosity improvers.

Although there are disclosures in the art of olefinic hydrocarbonsfunctionalized at the carbon-carbon double bond to form a carboxylicacid or derivative thereof via Koch-type chemistry, there is nodisclosure that polymers containing carbon-carbon double bonds,including terminal olefinic bonds, either secondary or tertiary typeolefinic bonds, could be successfully reacted via the Koch mechanism.Additionally, it has been found that the process of the presentinvention is particularly useful to make neo acid and neo esterfunctionalized polymer. Known catalysts used to carboxylate lowmolecular weight olefinic hydrocarbons by the Koch mechanism were foundto be unsuitable for use with polymeric material. Specific catalystshave been found which can result in the formation of a carboxylic acidor ester at a carbon-carbon double bond of a polymer. While Kochchemistry affords the advantage of the use of moderate temperatures andpressures, it requires highly acidic catalysts and careful control ofconcentrations.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the present invention, polymers comprising at leastone non-aromatic carbon-carbon double bond, also referred to as anethylenic or olefinic bond are reacted via a Koch mechanism with carbonmonoxide to form a carboxylic acid, carboxylic ester or thiol esterfunctional group at the carbon-carbon double bond. The functional groupcan have an iso or neo type.

As used herein the term "hydrocarbyl" denotes a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character within the context of thisinvention. Such radicals include the following:

(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted aromatic, aromatic-substituted aliphatic andalicyclic radicals, and the like, as well as cyclic radicals wherein thering is completed through another portion of the molecule (that is, thetwo indicated substituents may together form a cyclic radical). Suchradicals are known to those skilled in the art; examples include methyl,ethyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl,eicosyl, cyclohexyl, phenyl and naphthyl (all isomers being included).

(2) Substituted hydrocarbon groups; that is, radicals containingnon-hydrocarbon substituents which, in the context of this invention, donot alter the predominantly hydrocarbon character of the radical. Thoseskilled in the art will be aware of suitable substitutents (e.g., halo,hydroxy, alkoxy, carbalkoxy, nitro, alkylsulfoxy).

(3) Hetero groups; that is, radicals which, while predominantlyhydrocarbon in character within the context of this invention, containatoms other than carbon present in a chain or ring otherwise composed ofcarbon atoms. Suitable hetero atoms will be apparent to those skilled inthe art and include, for example, nitrogen particularly non-basicnitrogen which would not deactivate the Koch catalyst, oxygen andsulfur.

In general, no more than about three substituents or hetero atoms, andpreferably no more than one, will be present for each 10 carbon atoms inthe hydrocarbon-based radical.

According to the present invention, the Koch reaction has been appliedto polymers comprising at least one non-aromatic carbon-carbon doublebond. Carbon monoxide, or carbon monoxide from a carbon monoxide source,is reacted with a carbon atom of a carbon-carbon double bond in thepresence of a specifically selected acidic catalyst. In accordance withclassical proposed Koch mechanistic theory the addition of the acidiccatalyst results in the formation of a carbenium ion at thecarbon-carbon double bond. A proton from the acidic catalyst combineswith the double bond. There is subsequent addition of carbon monoxide tothe carbenium ion to result in an acylium cation. Where the carbeniumion is secondary an iso acylium cation is formed. Where the olefinicunsaturation is such that a tertiary carbocation is generated a neoacylium cation forms. The iso and neo acylium cations are then reactedwith what is referred to herein as a nucleophilic trapping agent, suchas, water, a hydroxyl group-containing compound, such as an alcohol or aphenolic compound, and/or a thiol, to form carboxylic acid, carboxylester, or thioester, respectively. The neo acid or esters which form areparticularly stable.

Following is an example of a terminally unsaturated polymer reacted viathe Koch mechanism to form an acid or an ester. The polymer is contactedwith carbon monoxide or a suitable carbon monoxide source such as formicacid in the presence of an acidic catalyst. The catalyst contributes aproton to the carbon-carbon double bond to form a carbenium ion. This isfollowed by addition of CO to form an acylium ion which reacts with thenucleophilic trapping agent. (POLY), R¹, R² and R³ are defined as above.##STR8##

The Koch reaction is particularly useful to functionalize poly(alphaolefins) and ethylene alpha olefin copolymers formed usingmetallocene-type catalysts. These polymers contain terminal vinylidenegroups. There is a tendency for such terminal groups to predominate andresult in neo-type (tertiary) carbenium ions. In order for the carbeniumion to form the acid catalysts must be relatively strong. However, thestrength of the acid catalyst must be balanced against detrimental sidereactions which can occur when the acid is too strong.

The Koch catalyst can be employed by preforming a catalyst complex withthe proposed nucleophilic trapping agent or by adding the catalyst andtrapping agent separately to the reaction mixture. This latterembodiment has been found to be a particular advantage since iteliminates the step of making the catalyst complex.

It has been determined that the Koch catalyst or catalyst complex of thepresent invention should have a Hammett Scale Value acidity (Ho) of lessthan -7 in order to be sufficiently active to react with a polymer,particularly to form neo structures. However, Hammett acidities of lessthan -12 can cause undesirable side reactions. Therefore, a preferredrange of Hammett acidity is from -8 to -11.5 and most preferably -10 to-11.5.

The following are acidic catalyst and catalyst complex materials andtheir respective Hammett Scale Value acidity: 60% H₂ SO₄, -4.32; BF₃.3H₂ O, -4.5; BF₃.2 H₂ O, -7.0; WO₃ /Al₂ O₃, less than -8.2; SiO₂ /Al₂ O₃,less than -8.2; HF, -10.2; BF₃.H₂ O, -11.4; -11.94; ZrO₂ less than-12.7; SiO₂ /Al₂ O₃, -12.7 to -13.6; AlCl₃, -13.16 to -13.75; AlCl₃/CuSO₄ -13.75 to -14.52.

It has been found that BF₃.2 H₂ O is ineffective at functionalizingpolymer through a Koch mechanism ion with polymers. In contrast, BF₃.H₂O resulted in high yields of carboxylic acid for the same reaction.

The use of H₂ SO₄ as a catalyst involves control of the acidconcentration to achieve the desired Hammett Scale Value range.Catalysts which are particularly useful for forming neo acids, are inthe preferred Hammett Scale Value range of -8 to -11.5, with preferredcatalysts being H₂ SO₄ and BF₃.

Suitable BF₃ catalyst complexes for use in the present invention can berepresented by the formula:

    BF.sub.3.xHOR

wherein R can represent hydrogen, hydrocarbyl (as defined below inconnection with R') ##STR9## and mixtures thereof wherein R' ishydrocarbyl, typically alkyl, e.g., C₁ to C₂₀ alkyl, and, e.g., C₆ toC₁₄ aryl, aralkyl, and alkaryl.

The carbenium ion reacts with CO to form acylium cation. The acyliumcation can be further reacted with water or another nucleophilictrapping agent such as an alcohol or phenolic, or thiol compound. Theuse of water releases the catalyst to form an acid. The use of hydroxytrapping agents releases the catalyst to form an ester, the use of athiol releases the catalyst to form a thio ester.

Koch product, also referred to herein as functionalized polymer,typically will be derivatized as described hereinafter. Derivatizationreactions involving ester functionalized polymer will typically have todisplace the alcohol derived moiety therefrom. Consequently, the alcoholderived portion of the Koch functionalized polymer is sometimes referredto herein as a leaving group. The ease with which a leaving group isdisplaced during derivatization will depend on its acidity, i.e. thehigher the acidity the more easily it will be displaced. The acidity inturn of the alcohol is expressed in terms of its pKa.

Preferred nucleophilic trapping agents include water and hydroxy groupcontaining compounds. Useful hydroxy trapping agents include aliphaticcompounds such as monohydric and polyhydric alcohols or aromaticcompounds such as phenols and naphthols. The aromatic hydroxy compoundsfrom which the esters of this invention may be derived are illustratedby the following specific example: phenol, -naphthol, cresol,resorcinol, catechol, 2-chlorophenol. Particularly preferred is2,4-dichlorophenol.

The alcohols preferably can contain up to about 40 aliphatic carbonatoms. They may be monohydric alcohols such as methanols, ethanol,isooctanol, dodecanol, cyclohexanol, cyclopentanol, neopentyl alcohol,isobutyl alcohol, benzyl alcohol, 2-methylcyclohexanol,beta-chloroethanol, monomethyl ether Of ethylene glycol. The polyhydricalcohols preferably contain from 2 to about 5 hydroxy radicals. They areillustrated by, for example, ethylene glycol, diethylene glycol. Otheruseful polyhydric alcohols include glycerol, monomethyl ether ofglycerol,and pentaerythritol.

Useful unsaturated alcohols include allyl alcohol, and propargylalcohol.

Particularly preferred alcohols include those having the formula R^(*) ₂CHOH where an R^(*) is independently hydrogen, an alkyl, aryl,hydroxyalkyl, or cycloalkyl. Specific alcohols include alkanols such asmethanol, ethanol, propanol, butanol, pentanol, hexanol as well as2-ethyl hexanol. Also preferred useful alcohols include aromaticalcohols, phenolic compounds and polyhydric alcohols as well asmonohydric alcohols such as 1,4-butanediol.

It has been found that neo-acid ester functionalized polymer, isextremely stable, due, it is believed to steric hindrance. Consequently,the yield of derivatized polymer obtainable therefrom will varydepending on the ease with which a derivatizing compound can displacethe leaving group of the functionalized polymer.

Accordingly, it has been found that the yield of derivatized polymer canbe significantly enhanced by controlling the acidity of the leavinggroup, e.g., the alcohol derived portion of the ester functionalizedpolymer. Thus, while any acidity which is effective to enable theleaving group --YR³ of Formula (I) to be displaced during derivatizationcan be employed, it is contemplated that such effective acidities,expressed as the pKa of the compound HYR³, be typically not greater thanabout 12, preferably not greater than about 10, and most preferably notgreater than about 8, which pKa values can range typically from about 5to about 12, preferably from about 6 to about 10, and most preferablyfrom about 6 to about 8.

The most preferred alcohol trapping agents can be obtained bysubstituting a phenol with at least one electron withdrawing substituentsuch that the substituted phenol possesses a pKa within the abovedescribed pKa ranges. In addition, phenol can also be substituted withat least one non-electron withdrawing substituent (e.g., electrondonating), preferably at positions meta to the electron withdrawingsubstituent to block undesired alkylation of the phenol by the polymerduring the Koch reaction. This further improves yield to desired esterfunctionalized polymer.

Accordingly, and in view of the above, the most preferred trappingagents are phenolic and substituted phenolic compounds represented bythe formula: ##STR10## wherein X, which may be the same or different, isan electron withdrawing substituent, and T which may be the same ordifferent is a non-electron withdrawing group; m and p are from 0 to 5with the sum of m and p being from 0 to 5, and m is preferably from 1 to5, and more preferably, m is 1 or 2. X is preferably a group selectedfrom halogen, cyano, and nitro, preferably located at the 2- and/or 4-position, and T is a group selected from hydrocarbyl, and hydroxy groupsand p is 1 or 2 with T preferably being located at the 4 and/or 6position. More preferably X is selected from C₁, F, Br, cyano or nitrogroups and m is preferably from 1 to 5, more preferably from 1 to 3, yetmore preferably 1 to 2, and most preferably 2 located at the 2 and 4locations relative to --OH.

The relative amounts of reactants and catalyst, and the conditions arecontrolled in a manner sufficient to functionalize typically at leastabout 40, preferably at least about 80, more preferably at least about90 and most preferably at least about 95 mole % of the carbon-carbondouble bonds initially present in the unfunctionalized polymer.

The amount of H₂ O, alcohol, or thiol used should be at least thestoichiometric amount required to react with the acylium cations. It ispreferred to use an excess of alcohol over the stoichiometric amount.The alcohol performs the dual role of reactant and diluent for thereaction. However, the amount of the alcohol or water used should besufficient to provide the desired yield yet at the same time not dilutethe acid catalyst so as to increase the Hammett Scale Value acidityabove -7.

The polymer added to the reactant system can be in a liquid phase.Optionally, the polymer can be dissolved in an inert solvent. The yieldcan be determined upon completion of the reaction by separating polymermolecules which contain acyl groups which are polar and hence can easilybe separated from unreacted non-polar compounds. Separation can beperformed using absorption techniques which are known in the art. Theamount of initial carbon-carbon double bonds and carbon-carbon doublebonds remaining after the reaction can be determined by C¹³ NMRtechniques.

In accordance with the process, the polymer is heated to a desiredtemperature range which is typically between -20° C. to 200° C.,preferably from 0° C. to 80° C. and more preferably from 40° C. to 65°C. Temperature can be controlled by heating and cooling means applied tothe reactor. Since the reaction is exothermic usually cooling means arerequired.

Mixing is conducted throughout the reaction to assure a uniform reactionmedium.

The catalyst (and nucleophilic trapping agent) can be prereacted to forma catalyst complex or are charged separately in one step to the reactorto form the catalyst complex in situ at a desired temperature andpressure, preferably under nitrogen. The nucleophilic trapping agent,preferably is a substituted phenol used in combination with BF₃. Thereactor contents are continuously mixed and then rapidly brought to adesired operating pressure using a high pressure carbon monoxide source.Useful pressures can be up to 20,000 psig, and typically will be atleast 300, preferably at least 800, and most preferably at least 1,000psig, and typically will range from 500 to 5,000 psig preferably from650 to 3,000 and most preferably from 650 to 2000 psig. The carbonmonoxide pressure may be reduced by adding a catalyst such as a coppercompound.

The catalyst to polymer molar ratio can range from 0.25 to 4, preferably0.5 to 2 and most preferably 0.75 to 1.3.

Preferably, the polymer, catalyst, nucleophilic trapping agent and COare fed to the reactor in a single step. The reactor contents are thenheld for a desired amount of time under the pressure of the carbonmonoxide. The reaction time can range up to 5 hours and typically 0.5 to4 and more typically from 1 to 2 hours. The reactor contents can then bedischarged and the product which is a Koch functionalized polymercomprising either a carboxylic acid or carboxylic ester or thiol esterfunctional groups separated. Upon discharge, any unreacted CO can bevented off. Nitrogen can be used to flush the reactor and the vessel toreceive the polymer.

Depending on the particular reactants employed, the functionalizedpolymer containing reaction mixture may be a single phase, a combinationof a partitionable polymer and acid phase or an emulsion with either thepolymer phase or acid phase being the continuous phase.

Upon completion of the reaction, the polymer is recovered by suitablemeans.

When the mixture is an emulsion, a suitable means can be used toseparate the polymer. A preferred means is the use of fluoride salts,such as sodium or ammonium fluoride in combination with an alcohol suchas butanol or methanol to neutralize the catalyst and phase separate thereaction complex. The fluoride ion helps trap the BF₃ complexed to thefunctionalized polymer and helps break emulsions generated when thecrude product is washed with water. Alcohols such as methanol andbutanol and commercial demulsifiers also help to break emulsionsespecially in combination with fluoride ions. Preferably, nucleophilictrapping agent is combined with the fluoride salt and alcohols when usedto separate polymers. The presence of the nucleophilic trapping agent asa solvent minimizes tranesterification of the functionalized polymer.

Where the nucleophilic trapping agent has a pKa of less than 12 thefunctionalized polymer can be separated from the nucleophilic trappingagent and catalyst by depressurization and distillation. It has beenfound that where the nucleophilic trapping agent has lower pKa's, thecatalyst, i.e. BF₃ releases more easily from the reaction mixture.

As indicated above, polymer which has undergone the Koch reaction isalso referred to herein as functionalized polymer. Thus, afunctionalized polymer is chemically modified to have at least onefunctional group present within its structure, which functional group iscapable of: (1) undergoing further chemical reaction (e.g.derivatization) with other material/or (b) imparting desirableproperties, not otherwise possessed by the polymer alone, absent suchchemical modification.

It will be observed from the discussion of formula I that the functionalgroup is characterized as being represented by the parentheticalexpression ##STR11## which expression contains the acyl group ##STR12##It will be understood that while the ##STR13## moiety is not added tothe polymer in the sense of being derived from a separate reactant it isstill referred to as being part of the functional group for ease ofdiscussion and description. Strictly speaking, it is the acyl groupwhich constitutes the functional group, since it is this group which isadded during chemical modification. Moreover, R¹ and R² represent groupsoriginally present on, or constituting part of, the 2 carbons bridgingthe double bond before functionalization. However, R¹ and R² wereincluded within the parenthetical so that neo acyl groups could bedifferentiated from iso acyl groups in the formula depending on theidentity of R¹ and R².

Characterization of the degree to which the polymer has beenfunctionalized is referred to herein as "functionality". Functionalityrefers generally to the average number of functional groups presentwithin the polymer structure per polymer chain. Thus, functionality canbe expressed as the average number of moles of functional groups per"mole of polymer". When said "mole of polymer" in the functionalityratio includes both functionalized and unfunctionalized polymer,functionality is referred to herein as F which corresponds to n ofFormula (I). When said "mole of polymer" includes only functionalizedpolymer, functionality is referred to herein as F^(*).

The distinction between F and F^(*) arises when not all the polymerchains present in the reaction mixture are functionalized, e.g., becausethey have no unsaturation. In this instance typical analyticaltechniques employed to determine F, will normally necessitateidentification of the weight fraction of functionalized polymer, basedon the total weight of polymer (functionalized+unfunctionalized) in thesample being analyzed for functionality. This weight fraction iscommonly referred to as Active Ingredient or AI. Since the determinationof AI is a separate analytical step, it can be more convenient toexpress functionality as F rather than F,. In any event, both F andF^(*) are alternate ways of characterizing the functionality.

As a general proposition, the polymer of the present invention can befunctionalized to any functionality effective to impart propertiessuitable for the end use contemplated.

Typically, where the end use of the polymer is for making dispersant,e.g. as derivatized polymer, the polymer will possess dispersant rangemolecular weights (Mn) as defined hereinafter and the functionality willtypically be significantly lower than for polymer intended for makingderivatized multifunctional V.I. improvers, where the polymer willpossess viscosity modifier range molecular weights (Mn) as definedhereinafter.

Accordingly, while any effective functionality can be imparted tofunctionalized polymer intended for subsequent derivatization, it iscontemplated that such functionalities, expressed as F, can be fordispersant end uses, typically not greater than about 3, preferably notgreater than about 2, and typically can range from about 0.5 to about 3,preferably from about 0.8 to about 2.0 (e.g. 0.8 to about 1).

Similarly, effective functionalities F for viscosity modifier end usesof derivatized polymer are contemplated to be typically greater thanabout 3, preferably greater than about 5, and typically will range fromabout 5 to about 10.

F and F, values can be interconnected using the AI which for polymers ofthe present invention typically are at least about 0.50, preferably from0.65 to 0.99, more preferably from 0.75 to 0.99, yet more preferably0.85 to 0.99. However, the upper limit of AI is typically from 0.90 to0.99, and more typically 0.90 to 0.95. Where AI is 1.0, F=F^(*).

End uses involving very high molecular weight polymers contemplatefunctionalities which can range typically greater than about 20,preferably greater than about 30, and most preferably greater than about40, and typically can range from about 20 to about 60, preferably fromabout 25 to about 55 and most preferably from about 30 to about 50.

POLYMERS

The polymers which are useful in the present invention are polymerscontaining at least one carbon-carbon double bond (olefinic orethylenic) unsaturation. Thus, the maximum number of functional groupsper polymer chain is limited by the number of double bonds per chain.Such polymers have been found to be receptive to Koch mechanisms to formcarboxylic acids or derivatives thereof, using the catalysts andnucleophilic trapping agents of the present invention.

Useful polymers in the present invention include polyalkenes includinghomopolymer, copolymer (used interchangably with interpolymer) andmixtures. Homopolymers and interpolymers include those derived frompolymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2to about 6 carbon atoms. The interpolymers are those in which two ormore olefin monomers are interpolymerized according to well-knownconventional procedures to form polyalkenes having units within theirstructure derived from each of said two or more olefin monomers. Thus,"interpolymer(s)" as used herein is inclusive of terpolymers,tetrapolymers and the like. As will be apparent to those of ordinaryskill in the art, the polyalkenes from which the poly-substituent ofFormula I are derived are often conventionally referred to as"polyolefin(s)".

Useful polymers include those described in U.S. Pat. Nos. 4,234,435,5,017,299 and EP 0,462,319-A1, all hereby incorporated by reference.Particular reference is made to the alpha olefin polymers disclosed tobe made using organo metallic coordination compounds. A particularlypreferred class of polymers are ethylene alpha olefin copolymers such asthose disclosed in U.S. Pat. No. 5,017,299, hereby incorporated byreference.

The polymers for use in this invention possess at least onecarbon-carbon unsaturated double bond. The unsaturation can be terminal,internal or both. Preferred polymers have terminal unsaturation. Thepolymers of the present invention preferably comprise a high degree ofterminal unsaturation. Terminal unsaturation is the unsaturationprovided by the last monomer unit located in the polymer. Theunsaturation can be located anywhere in this terminal monomer unit.Terminal olefinic groups include vinylidene unsaturation, R^(a) R^(b)C═CH₂ ; trisubstituted olefin unsaturation, R^(a) R^(b) C═CR^(c) H;vinyl unsaturation, R^(a) HC═CH₂ ; 1,2-disubstituted terminalunsaturation, R^(a) HC═CHR^(b) ; and tetra-substituted terminalunsaturation, R^(a) R^(b) C═CR^(c) R^(d). At least one of R^(a) andR^(b) is a polymeric group of the present invention, and the remainingR^(b), R^(c) and R^(d) are hydrocarbon groups as defined with respect toR, R¹, R², and R³ above.

The homopolymers and copolymers of the present invention can beconveniently characterized based on molecular weight range. Polymers andcopolymers of low, intermediate and high molecular weights can beprepared.

Low molecular weight polymers, also referred to herein as dispersantrange molecular weight polymers, are considered to be polymers having anumber average molecular weight of less than 20,000, preferably fromabout 500 to about 20,000 (e.g. 1,000 to 20,000), more preferably fromabout 1,500 to about 10,000 (e.g. 2,000 to 8,000) and most preferablyfrom 1,500 to 5,000. The low molecular weights are number averagemolecular weights measured by vapor phase osmometry. Low molecularweight polymers are useful in forming dispersants for lubricantadditives

Medium molecular weight polymers, also referred to herein as viscositymodifier range molecular weight polymers, have number average molecularweights ranging from 20,000 to 200,000, preferably 25,000 to 100,000;and more preferably, from 25,000 to 80,000 are useful for viscosityindex improvers for lubricating oil compositions, adhesive coatings,tackifiers and sealants. The medium number average molecular weights canbe determined by membrane osmometry.

The higher molecular weight materials have a number average molecularweight of greater than about 200,000 and can range from 201,000 to15,000,000, and specific embodiment of 300,000 to 10,000,000 and morespecifically 500,000 to 2,000,000. These polymers are useful inpolymeric compositions and blends including elastomeric compositions.Higher molecular weight materials having number average molecularweights of from 20,000 to 15,000,000 can be measured by gel permeationchromatography with universal calibration, or by light scattering asrecited in Billmeyer, Textbook of Polymer Science, Second Edition, pp.81-84 (1971).

The values of the ratio Mw/Mn, also referred to as molecular weightdistribution, (MWD) are not critical. However, a typical minimum Mw/Mnvalue of about 1.1-2.0 is preferred with typical ranges of about 1.1 upto about 4.

Useful olefin monomers from which the polyalkenes can be derived arepolymerizable olefin monomers characterized by the presence of one ormore unsaturated double bonds (i.e., >C═C<); that is, they aremonoolefinic monomers such as ethylene, propylene, butene-1, isobutene,and octene-1 or polyolefinic monomers (usually diolefinic monomers) suchas butadiene-1,3 and isoprene.

The polymer used in the invention can be derived from the polymerizationof monomers selected from the group consistin of olefin, diolefin andmixtures to form homopolymers or copolymers.

These olefin monomers are preferably polymerizable terminal olefins;that is, olefins characterized by the presence in their structure of thegroup ##STR14## where R' is H or a hydrocarbon group. However,polymerizable internal olefin monomers (sometimes referred to in thepatent literature as medial olefins) characterized by the presencewithin their structure of the group: ##STR15## can also be used to formthe polyalkenes. When internal olefin monomers are employed, theynormally will be employed with terminal olefins to produce polyalkeneswhich are interpolymers. For purposes of this invention, when aparticular polymerized olefin monomer can be classified as both aterminal olefin and an internal olefin, it will be deemed to be aterminal olefin. Thus, pentadiene-1,3 (i.e., piperylene) is deemed to bea terminal olefin for purposes of this invention.

While the polyalkenes generally are hydrocarbon polyalkenes, they cancontain substituted hydrocarbon groups such as lower alkoxy, lower alkylmercapto, hydroxy, mercapto, and carbonyl, provided the non-hydrocarbonmoieties do not substantially interfere with the functionalization orderivatization reactions of this invention. When present, suchsubstituted hydrocarbon groups normally will not contribute more thanabout 10% by weight of the total weight of the polyalkenes. Since thepolyalkene can contain such non-hydrocarbon substituent, it is apparentthat the olefin monomers from which the polyalkenes are made can alsocontain such substituents. Normally, however, as a matter ofpracticality and expense, the olefin monomers and the polyalkenes willbe free from non-hydrocarbon groups. (As used herein, the term "lower"when used with a chemical group such as in "lower alkyl" or "loweralkoxy" is intended to describe groups having up to seven carbon atoms.)

Although the polyalkenes may include aromatic groups (especially phenylgroups and lower alkyl- and/or lower alkoxy-substituted phenyl groupssuch as para-(tert-butyl)phenyl) and cycloaliphatic groups such as wouldbe obtained from polymerizable cyclic olefins or cycloaliphaticsubstituted-polymerizable acyclic olefins, the polyalkenes usually willbe free from such groups. Again, because aromatic and cycloaliphaticgroups can be present, the olefin monomers from which the polyalkenesare prepared can contain aromatic and cycloaliphatic groups.

There is a general preference for polyalkenes free from aromatic andcycloaliphatic groups (other than the diene styrene interpolymerexception already noted). Within this general preference, there is afurther preference for polyalkenes which are derived from the groupconsisting of homopolymers and interpolymers of terminal hydrocarbonolefins of 2 to about 16 carbon atoms. This further preference isqualified by the proviso that, while interpolymers of terminal olefinsare usually preferred, interpolymers optionally containing up to about40% of polymer units derived from internal olefins of up to about 16carbon atoms are also within a preferred group. A more preferred classof polyalkenes are those selected from the group consisting ofhomopolymers and interpolymers of terminal olefins of 2 to about 6carbon atoms, more preferably 2 to 4 carbon atoms. However, anotherpreferred class of polyalkenes are the latter, more preferredpolyalkenes optionally containing up to about 25% of polymer unitsderived from internal olefins of up to about 6 carbon atoms.

Specific examples of terminal and internal olefin monomers which can beused to prepare the polyalkenes according to conventional, well-knownpolymerization techniques include ethylene; propylene; butene-1;butene-2; isobutene; pentene-1; hexene-1; heptene-1; octene-1; nonene-1;decene-1; pentene-2; propylene-tetramer; diisobutylene; isobutylenetrimer; butadiene-1,2; butadiene-1,3; pentadiene-1,2; pentadiene-1,3;pentadiene-1,3; isoprene; hexadiene-1,5; 2-chlorobutadiene-1,2;2-methyl-heptene-1; 3-cyclohexylbutene-1; 2-methyl-5-propyl-hexene-1;pentene-3; octene-4; 3,3-dimethyl-pentene-1; styrene;2,4-dichlorostyrene; divinylbenzene; vinyl acetate; allyl alcohol;1-methyl-vinyl acetate; acrylonitrile; ethyl acrylate; methylmethacrylate; ethyl vinyl ether; and methyl vinyl ketone. Of these, thehydrocarbon polymerizable monomers are preferred and of thesehydrocarbon monomers, the terminal olefin monomers are particularlypreferred.

Useful polymers include alpha-olefin homopolymers and interpolymers, andethylene alpha-olefin copolymers and terpolymers. Specific examples ofpolyalkenes include polypropylenes, polybutenes, ethylene-propylenecopolymers, ethylene-butene, propylene-butene copolymers,styrene-isobutene copolymers, isobutene-butadiene-1,3 copolymers,propene-isoprene copolymers, isobutenechloroprene copolymers,isobutene-(paramethyl)styrene copolymers, copolymers of hexene-1 withhexadiene-1,3, copolymers of octene-1, copolymers of3,3-dimethyl-pentene-1 with hexene-1, and terpolymers of isobutene,styrene and piperylene. More specific examples of such interpolymersinclude copolymer of 95% (by weight) of isobutene with 5% (by weight) ofstyrene; terpolymer of 98% of isobutene with 1% of piperylene and 1% ofchloroprene; terpolymer of 95% of isobutene with 2% of butene-1 and 3%of hexene-1; terpolymer of 60% of isobutene with 20% of pentene-1; and20% of octene-1; terpolymer of 90% of isobutene with 2% of cyclohexeneand 8% of propylene; and copolymer of 80% of ethylene and 20% ofpropylene. A useful source of polyalkenes are the poly(isobutene)sobtained by polymerization of C₄ refinery stream having a butene contentof about 35 to about 75% by wt and an isobutene content of about 30 toabout 60% by wt in the presence of a Lewis acid catalyst such asaluminum trichloride or boron trifluoride.

Useful ethylne alpha-olefin copolymers include copolymrs of ethylene,alpha-olefin and a nonconjugated polyene. Illustrative of suchnonconjugated polyenes are aliphatic dienes such as 1,4-hexadiene,1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene,3-methyl-1,4-hexadiene, 4-methyl-1,3-hexadiene, 1,7-octadiene,1,9-decadiene, exo and endodicyclopentadiene and the like, exo- andendo-alkenylnorbornenes, sucha s 5-propenyl-, 5-(buten-2-yl)-, and5-(2-methylbuten-[2']-yl)norbornene and the like;alkylalkenylnorbornenes, such as 5-methyl-6-propenyl-norbornene and thelike; alkylidenenorbornenes, such as 5-methylene-, 5-ethylidene-, and5-isopropylidene-2-norbornene, vinylnorbornene, cyclohexenylnorborneneand teh like; alkylnorbornadienes, such as methyl-, ethyl-, andpropylnorbornadiene and the like; and cyclodienes such as1,5-cyclooctadiene, 1,4-cyclooctadiene and the like.

Also useful are high molecular weight poly-n-butenes. Reference is madeto commonly assigned copending U.S. Ser. No. 992,871, filed Dec. 17,1992 (Docket No. PT-915) entitled, "Amorphous Olefin Polymers,Copolymers, Methods of Preparation and Derivatives Thereof"; hereinincorporated by reference.

A preferred source of monomer for making poly-n-butenes is petroleumfeedstreams such as Raffinate II. These feedstocks are disclosed in theart such as in U.S. Pat. No. 4,952,739, hereby incorporated byreference.

Preparing polyalkenes as described above which meet the various criteriafor Mn and Mw/Mn is within the skill of the art and does not comprisepart of the present invention. Techniques readily apparent to thoseskilled in the art include controlling polymerization temperatures,regulating the amount and type of polymerization initiator and/orcatalyst, employing chain terminating groups in the polymerizationprocedure, and the like. Other conventional techniques such as stripping(including vacuum stripping) a very light end and/or oxidatively ormechanically degrading high molecular weight polyalkene to produce lowermolecular weight polyalkenes can also be used.

ETHYLENE ALPHA-OLEFIN COPOLYMER

Preferred polymers are polymers of ethylene and at least onealpha-olefin having the formula H₂ C═CHR⁴ wherein R⁴ is straight chainor branched chain alkyl radical comprising 1 to 18 carbon atoms andwherein the polymer contains a high degree of terminal ethenylideneunsaturation. Preferably R⁴ in the above formula is alkyl of from 1 to 8carbon atoms and more preferably is alkyl of from 1 to 2 carbon atoms.Therefore, useful comonomers with ethylene in this invention includepropylene, 1-butene, hexene-1, octene-1, 4-methylpentene-1, decene-1,dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1,heptadecene-1, octadecene-1, nonadecene-1 and mixtures thereof (e.g.mixtures of propylene and 1-butene, and the like). Preferred polymersare copolymers of ethylene and propylene and ethylene and butene-1.

The molar ethylene content of the polymers employed is preferably in therange of between about 20 and about 80%, and more preferably betweenabout 30 and about 70%. When butene-1 is employed as comonomer withethylene, the ethylene content of such copolymer is most preferablybetween about 20 and about 45 wt %, although higher or lower ethylenecontents may be present.

The most preferred ethylene-butene-1 copolymers are disclosed incommonly assigned U.S. Ser. No. 992,192, filed Dec. 17, 1992, titledPOLYMERS DERIVED FROM ETHYLENE AND 1-BUTENE FOR USE IN THE PREPARATIONOF LUBRICANT DISPERSANT ADDITIVES (Docket No. PT-944).

The preferred method for making low molecular weight ethylene/α-olefincopolymer is described in commonly assigned U.S. Ser. No. 992,690, filedDec. 17, 1992, titled DILUTE FEED PROCESS FOR THE POLYMERIZATION OFETHYLENE/α-OLEFIN USING METALLOCENE CATALYST SYSTEMS (Docket No.PT-937). The disclosure of the above two patent applications are hereinincorporated by reference.

The ethylene alpha-olefin polymers generally possess a number averagemolecular weight as recited. Preferred ranges of molecular weights ofpolymer for use as precursors for dispersants of from about 500 to about10,000, preferably of from about 1,000 to about 8,000, most preferablyof from about 2,500 to about 6,000. The number average molecular weightfor such polymers can be determined by several known techniques. Aconvenient method for such determination is by size exclusionchromatography (also known as gel permeation chromatography (GPC)) whichadditionally provides molecular weight distribution information, see W.W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion LiquidChromatography", John Wiley and Sons, New York, 1979. Such polymersgenerally possess an intrinsic viscosity (as measured in tetralin at135° C.) of between about 0.025 and about 0.6 dl/g, preferably ofbetween about 0.05 and about 0.5 dl/g, most preferably of between about0.075 and about 0.4 dl/g. These polymers preferably exhibit a degree ofcrystallinity such that, when grafted, they are essentially amorphous.

The preferred ethylene alpha-olefin polymers are further characterizedin that up to about 95% and more of the polymer chains possess terminalvinylidene-type unsaturation. Thus, one end of such polymers will be ofthe formula POLY-C(R^(e))═CH₂ wherein R^(e) is C₁ to C₁₈ alkyl,preferably C₁ to C₈ alkyl, and more preferably C₁ to C₂ alkyl, (e.g.,methyl or ethyl) and wherein POLY represents the polymer chain. Thechain length of the R^(e) alkyl group will vary depending on thecomonomer(s) selected for use in the polymerization. A minor amount ofthe polymer chains can contain terminal ethenyl unsaturation, i.e.POLY--CH═CH₂, and a portion of the polymers can contain internalmonounsaturation, e.g. POLY--CH═CH(R^(e)), wherein R^(e) is as definedabove.

The ethylene alpha-olefin polymer comprises polymer chains, at leastabout 30% of which possess terminal vinylidene unsaturation. Preferablyat least about 50%, more preferably at least about 60%, and mostpreferably at least about 75% (e.g. 75 to 98%), of such polymer chainsexhibit terminal vinylidene unsaturation. The percentage of polymerchains exhibiting terminal vinylidene unsaturation may be determined byFTIR spectroscopic analysis, titration, HNMR, or C¹³ NMR.

The ethylene alpha-olefin polymer and the compositions employed in thisinvention may be prepared as described in U.S. Pat. No. 4,668,834, inEuropean Patent Publications 128,046 and 129,368, and in co-pending Ser.No. 728,111, filed Apr. 29, 1985, and Ser. No. 93,460, filed Sep. 10,1987, now U.S. Pat. No. 5,084,534, the disclosures all of which arehereby incorporated by reference in their entirety.

The polymers can be prepared by polymerizing monomer mixtures comprisingethylene in combination with other monomers such as alpha-olefins havingfrom 20 carbon atoms (and preferably from 3 to 4 carbon atoms, i.e.,propylene, butene-1, and mixtures thereof) in the presence of ametallocene catalyst system comprising at least one metallocene (e.g., acyclopentadienyl-transition metal compound) and an activator, e.g.alumoxane compound. The comonomer content can be controlled through theselection of the metallocene catalyst component and by controlling thepartial pressure of the various monomers.

The, polymer for use in the present invention can include block andtapered copolymers derived from monomers comprising at least oneconjugated diene with at least monovinyl aromatic monomer, preferablystyrene. Useful polymers include polymers of the type disclosed in U.S.Pat. Nos. 4,073,737 and 3,795,615, both hereby incorporated byreference.

Such polymers should not be completely hydrogenated so that thepolymeric composition contains olefinic double bonds, preferably atleast one bond per molecule. Useful polymers include an oil solublecopolymer of the following general formula:

    (A).sub.x (B).sub.y                                        (4)

wherein:

A is a conjugated diene of the formula: ##STR16## wherein R^(f) is a Hor C₁ to C₈ alkyl group, preferably H or CH₃, i.e. isoprene, and presentin mole % proportion as indicated by x which may vary from 45 to 99 mole%;

B is a C₈ to C₂₀ monovinyl aromatic compound and/or aromatic substituteddiene and present in weight % proportion as indicated by y which mayvary from 1 to 55 mole %; preferably 5 to 40 mole %, and optionally 25to 30 mole % whereby the most useful composite properties of oxidativestability and -18° C. viscosity of the lubricating oil blend isrealized.

The copolymers and block copolymers may be conveniently prepared withknown metallic or organometallic catalysts such as lithium metal orsodium metal and organo-lithium or organo-sodium catalysts.

The solution copolymerization may be carried out at any desiredtemperature in the range from -50° C. to +150° C., and is preferablyeffected at a temperature between -20° C. and +80° C. The solvents usedin polymerization are, in preferred form, hydrocarbon solvents such aspentane, hexane, heptane, cyclohexane, benzene, toluene, xylene andethyl benzene, with benzene and hexane being the preferred species.

The molecular weight of the copolymers of the mixed conjugated dienesand the monovinyl aromatic monomer may vary between wide limits, asdescribed above depending on intended end use.

The (Mn) is regulated by the ratio of the number of moles of catalyst(e.g., butyllithium) to the number of moles of monomers present duringpolymerization; the number of units originating from the monomers in apolymer molecule is substantially equal to the ratio of the number ofmoles of monomer to the number of moles of catalyst (assuming that eachcatalyst molecule contains one alkali metal atom) present duringpolymerization, provided that no contaminants which give rise to sidereactions with the catalyst (such as oxygen, water, carbon dioxide) arepresent. If single block copolymers are coupled together, the multipleblock copolymers formed have molecular weights which can be calculatedfrom the molecular weight of the single block copolymers (determined asabove) and the number thereof which are coupled together.

When the copolymerization has been completed, the block copolymer thusobtained can be partially hydrogenated either immediately or afterrecovery.

Methods of hydrogenation well known to one skilled in the art areapplicable.

Block copolymers as used herein includes "multiple block copolymers"which term denotes copolymers consisting of two or more of the singleblock copolymers described above, which are bound to each other. Amultiple block copolymer may, for example, be prepared by firstcopolymerizing to completion a mixture of butadiene and isoprene,thereafter polymerizing styrene onto said copolymer and subsequentlysequentially copolymerizing a mixture of butadiene and isoprene followedby said styrene onto the "living" block copolymer. For purposes of thisdisclosure, a "living" copolymer is one which remains stable over anextended period of time during which additional monomers can be added toit.

Multiple block copolymers can also be obtained in other ways such as bycoupling of two or more "living" block copolymer molecules. This can beachieved by addition of a compound which reacts with two or more"living" single block copolymer molecules. Examples of this type ofcompound include compounds containing two or more ester groups,compounds with more than one active halogen atom, e.g., di- andtri-chloromethyl-benzene, phosgene, dichlorosilane, carbontetrachloride, dimethyldichlorosilane, 1,2-dichloroethane,1,2-dibromomethane, and the like. Another possible method for preparingmultiple block copolymers consists in the preparation of single blockcopolymer containing a reactive group in the molecule (e.g., a carboxylgroup, which is, for example, obtained by bringing the polymerization ofa single copolymer to an end by addition of carbon dioxide) and couplingof two or more of the molecules, e.g., by esterifying them with a di- orpolyvalent alcohol. Multiple block copolymers have the further advantagethat they can be tailored to provide the most useful additive propertieswhile masking one or more undesirable properties inherent in any polymerblock.

The present invention can also include star polymers as disclosed inpatents such as U.S. Pat. Nos. 5,070,131; 4,108,945 and 3,711,406 aswell as 5,049,294. Particularly useful star polymers are disclosed inU.S. Pat. No. 5,070,131.

Useful star polymers can be produced by the process comprising thefollowing reaction steps:

(a) polymerizing one or more conjugated dienes and, optionally, one ormore monoalkenyl arene compounds, in solution, in the presence of anionic initiator to form a living polymer;

(b) reacting the living polymer with a polyalkenyl coupling agent toform a star-shaped polymer; and

(c) partially hydrogenating the star-shaped polymer. The living polymersproduced in reaction step (a) are the precursors of thepartiallyhydrogenated polymer chains which extend outwardly from thepoly(polyalkenyl coupling agent) nucleus.

Living polymers may be prepared by anionic solution polymerization ofconjugated dienes and, optionally, monoalkenyl arene compounds in thepresence of an alkali metal or an alkali-metal hydrocarbon, e.g. sodiumnaphthalene, as an ionic initiator. The preferred initiator is lithiumor a monolithium hydrocarbon.

The living polymers obtained by reaction step (a), which are linearunsaturated living polymers, are prepared from one or more conjugateddienes, e.g. C₄ to C₁₂ conjugated dienes and, optionally, one or moremonoalkenyl arene compounds.

Examples of suitable conjugated dienes include butadiene(1,3-butadiene);isoprene; 1,3-pentadiene (piperylene); 2,3-dimethyl-1,3-butadiene;3-butyl-1,3-octadiene; 1-phenyl-1,3-butadiene; 1,3-hexadiene; and4-ethyl-1,3-hexadiene with butadiene and/or isoprene being preferred.Apart from the one or more conjugated dienes the living polymers mayalso be partly derived from one or more monoalkenyl arene compounds.

Preferred monoalkenyl arene compounds are the monovinyl aromaticcompounds such as styrene, monovinylnaphthalene as well as the alkylatedderivatives thereof such as o-, m- and p-methylstyrene,alphamethylstyrene and tertiary-butylstyrene. Styrene is the preferredmonoalkenyl arene compound due to its wide availability at a reasonablecost. If a monoalkenyl arene compound is used in the preparation of theliving polymers it is preferred that the amount thereof be below about50% by weight, preferably about 3% to about 50%.

The living polymers may also be partly derived from small amounts ofother monomers such as monovinylpyridines, alkyl esters of acrylic andmethacrylic acids (e.g. methyl methacrylate, dodecyclmethacrylate,octadecyclmethacrylate), vinyl chloride, vinylidene chloride, monovinylchloride, vinylidene chloride, monovinyl esters of carboxylic acids(e.g. vinyl acetate and vinyl stearate).

The living polymers may be living homopolymers, living copolymers,living terpolymers, living tetrapolymers, etc. The living homopolymersmay be represented by the formula A-M, wherein M is a carbanionic group,e.g. lithium, and A is polybutadiene or polyisoprene. Living polymers ofisoprene are the preferred living homopolymers. The living copolymersmay be represented by the formula A-B-M, wherein A-B is a block, randomor tapered copolymer such as poly(butadiene/isoprene),poly(butadiene/styrene) or poly(isoprene/styrene). Such formulae,without further restriction, do not place a restriction on thearrangement of the monomers within the living polymers. For example,living poly(isoprene/styrene) copolymers may be livingpolyisoprene-polystyrene block copolymers, livingpolystyrene-polyisoprene block copolymers, living poly(isoprene/styrene)random copolymers, living poly(isoprene/styrene)tapered copolymers orliving poly(isoprene/styrene/isoprene) block copolymers. Livingpoly(butadiene/styrene/isoprene) terpolymer is an example of a livingterpolymer which is acceptable.

The living copolymers may be living block copolymers, living randomcopolymers or living tapered copolymers. The living block copolymer maybe prepared by the step-wise polymerization of the monomers e.g.styrene, to form a living block copolymer having the formulapolyisoprene-polystyrene-M, or styrene may be polymerized first to formliving polystyrene followed by addition of isoprene to form a livingblock copolymer having the formula polystyrene-polyisoprene-M.

In one embodiment, the arms are diblock arms having conjugated diolefinouter blocks and monoalkenyl arene inner blocks. The arms are thereforepolymerized by polymerizing blocks of conjugated diolefins, and thenpolymerizing blocks of monoalkenyl arenes. The arms would then becoupled at the end of the monoalkenyl arene blocks.

Increasing the number of arms employed in star polymers significantlyimproves both the thickening efficiency and the shear stability of thepolymer since it is then possible to prepare additives having arelatively high molecular weight (resulting in increased thickeningefficiency) without the necessity of excessively long arms (resulting inan acceptable shear stability).

Star-shaped polymers, which are still "living", may then be deactivatedor "killed", in known matter, by the addition of a compound which reactswith the carbanionic end group. As examples of suitable deactivators maybe mentioned, compounds with one or more active hydrogen atoms such aswater, alcohols (e.g. methanol, ethanol isopropanol, 2-ethylhexanol) orcarboxylic acids (e.g. acetic acid), compounds with one active halogenatoms, e.g. a chlorine atom (e.g. benzyl chloride, chloromethane),compounds with one ester group and carbon dioxide. If not deactivated inthis way, the living star-shaped polymers may be killed byhydrogenation.

Before being killed, the living star-shaped polymers may be reacted withfurther amounts of monomers such as the same or different dienes and/ormonoalkenyl arene compounds of the types discussed above. The effect ofthis additional step, apart from increasing the number of polymerchains, is to produce a further living star-shaped polymer having atleast two different types of polymer chains. For example, a livingstar-shaped polymer derived from living polyisoprene may be reacted withfurther isoprene monomer to produce a further living star-shaped polymerhaving polyisoprene chains of different number average molecularweights. Alternatively, the living star-shaped polyisoprene homopolymermay be reacted with styrene monomer to produce a further livingstar-shaped copolymer having both polyisoprene and polystyrenehomopolymer chains. Thus it can be seen that by different polymer chainsis meant chains of different molecular weights and/or chains ofdifferent structures.

The star-shaped polymers can be hydrogenated by any suitable technique.Suitably not greater than 80%, of the original olefinic unsaturation ishydrogenated. If the star-shaped polymer is partly derived from amonoalkenyl arene compound, then the amount of aromatic unsaturationwhich is hydrogenated, if any, will depend on the hydrogenationconditions used. However, preferably less than 10%, more preferably lessthan 5% of such aromatic unsaturation is hydrogenated.

A preferred hydrogenation process is the selective hydrogenation processshown in U.S. Pat. No. 3,595,942, incorporated herein by reference.

DERIVATIZED POLYMERS

The Koch or functionalized polymer can be used as a dispersantmultifunctional viscosity modifier if the functional group contains therequisite polar group. The functional group can also enable the polymerto participate in a variety of chemical reactions. Derivatives offunctionalized polymers can be formed through reaction of the functionalgroup. These derivatized polymers have the requisite properties for avariety of uses including use as dispersants and viscosity modifiers.

A derivatized polymer is one which has been chemically modified toperform one or more functions in a significantly improved way relativeto the unfunctionalized polymer and/or the functionalized polymer.Representative of such functions, are dispersancy and/or viscositymodification in lubricating oil compositions.

More specifically, the functionalized polymer can be derivatized byreaction with at least one derivatizing compound to form derivatizedpolymers. The derivatizing compound typically contains at least onereactive derivatizing group. The reactive derivatizing group istypically selected to render it capable of reacting with the functionalgroups of the functionalized polymers by the various reactions describedbelow. Representative of such reactions are nucleophilic substitution,transesterification, salt formation, and the like. The derivatizingcompound preferably also contains at least one additional group suitablefor imparting the desired properties to the derivatized polymer, e.g.,polar groups. Thus, such derivatizing compounds typically will containone or more groups including amine, hydroxy, ester, amide, imide, thio,thioamido, oxazoline, or carboxylate groups or form such groups at thecompletion of the derivatization reaction.

Thus, the derivatized polymers can include the reaction product of theabove recited functionalized polymer with a nucleophilic reactant whichinclude amines, alcohols, amino-alcohols and mixtures thereof to formoil soluble salts, amides, oxazoline, and esters. Alternatively, thefunctionalized polymer can be reacted with basic metal salts to formmetal salts of the polymer. Preferred metals are Ca, Mg, Cu, Zn, Mo, andthe like.

Suitable properties sought to be imparted to the derivatized polymerinclude one or more of dispersancy, multifunctional viscositymodification, antioxidancy, friction modification, antiwear, antirust,seal swell, and the like.

The preferred properties sought to be imparted to the derivatizedpolymer include dispersancy (both mono- and multifunctional) viscositymodification (e.g. primarily viscosity modification with attendantsecondary dispersant properties). A multifunctional dispersant typicallywill function primarily as a dispersant with attendant secondaryviscosity modification.

As indicated above, dispersants are made from polymer having dispersantrange molecular weights and viscosity modifiers are made from polymerhaving viscosity modifier range molecular weights which are higher thandispersant range molecular weights.

Multifunctional dispersants rely on polymers having number averagemolecular weights of greater than about 2,000 to less than about 20,000.In short, the higher the Mn of the polymer within the dispersant rangemolecular weight, the higher the contribution of the polymer to the hightemperature viscosity properties of the formulation containing thedispersant.

Multifunctional viscosity modifiers possess attendant dispersantproperties when the polymer from which they are derived isfunctionalized and derivatized with groups which contribute todispersancy as described hereinafter in connection with ashlessdispersants.

However, while the Koch functionalization and derivatization techniquesfor preparing multifunctional viscosity modifiers (also referred toherein as multifunctional viscosity index improvers or MFVI) are thesame as for ashless dispersants, the functionality of a functionalizedpolymer intended for derivatization and eventual use as an MFVI will becontrolled to be higher than functionalized polymer intended foreventual use as a dispersant. This stems from the difference in Mn ofthe MFVI polymer backbone vs. the Mn of the dispersant polymer backbone.

Accordingly, it is contemplated that an MFVI will be derived fromfunctionalized polymer composition having typically up to about one andat least about 0.5 functional group F, (i.e. "n" of formula (I)) foreach 20,000, preferably for each 10,000, most preferably for each 5,000Mn molecular weight segment in the backbone polymer. For example, thefunctionality of a functionalized polymer having an Mn of 30,000 willtypically be controlled to have a functionality, F of about 6 (i.e.n=6). Consequently, the stoichiometry of the derivatization reactions isadjusted accordingly in view of the higher functionality relative to thestoichiometrics described below for dispersant derivatization.

Moreover, it will be observed that to achieve the higher functionalityfor MFVI end use the functionalization technique is also adjustedaccordingly. For example, to increase the functionality it may benecessary to incorporate additional sites of unsaturation into thepolymer. This can be achieved by incorporation of dienes into thepolymer.

Accordingly, while the following discussion relates primarily toderivatization for dispersant end use, the ashless dispersant portionthereof is also applicable to derivatization for MFVI end use subject tothe above caveats.

DISPERSANTS

Dispersants maintain oil insolubles, resulting from oxidation duringuse, in suspension in the fluid thus preventing sludge flocculation andprecipitation. Suitable dispersants include, for example, dispersants ofthe ash-producing (also known as detergent/inhibitors) and ashless type,the latter type being preferred.

The derivatized polymer compositions of the present invention, can beused as ashless dispersants and multifunctional viscosity indeximprovers in lubricant and fuel compositions. Ashless dispersants andviscosity index improvers are referred to as being ashless despite thefact that, depending on their constitution, the dispersants may, uponcombustion, yield a non-volatile material such as boric oxide orphosphorus pentoxide. The compounds useful as ashless dispersantsgenerally are characterized by a "polar" group attached to a relativelyhigh molecular weight hydrocarbon chain supplied by the polymer of thepresent invention. The "polar" group generally contains one or more ofthe elements nitrogen, oxygen and phosphorus. The solubilizing chainsare generally higher in molecular weight than those employed with themetallic based dispersants, but in some instances they may be quitesimilar.

Various types of ashless dispersants can be made by derivatizing thepolymer of the present invention and are suitable for use in thelubricant compositions.

Reaction products of functionalized polymer of the present inventionderivatized with nucleophilic reagents such as amine compounds, organichydroxy compounds such as polyols and/or basic inorganic materials.

At least one functionalized polymer is mixed with at least one of amine,alcohol, including polyol, aminoalcohol, etc., to form the dispersantadditives, One class of particularly preferred dispersants includesthose derived from the functionalized polymer of the present inventionreacted with (i) hydroxy compound, e.g., a polyhydric alcohol orpolyhydroxy-substituted aliphatic primary amine, e.g., pentaerythritolor trismethylolaminomethane (ii) polyoxyalkylene polyamine, e.g.polyoxypropylene diamine, and/or (iii) polyalkylene polyamine, e.g.,polyethylene diamine or tetraethylene pentamine referred to herein asTEPA.

DERIVATIZED POLYMER FROM AMINE COMPOUNDS

Useful amine compounds for derivatizing functionalized polymers compriseat least one amine and can comprise one or more additional amine orother reactive or polar groups. Where the functional group is acarboxylic acid, carboxylic ester or thiol ester, it reacts with theamine to form an amide.

Amine compounds useful as nucleophilic reactants for reaction with thefunctionalized polymer of the present invention include those disclosedin U.S. Pat. Nos. 3,445,441, 5,017,299 and 5,102,566, all herebyincorporated by reference. Preferred amine compounds include mono- and(preferably) polyamines, of about 2 to 60, preferably 2 to 40 (e.g. 3 to20), total carbon atoms of about 1 to 12, preferably 3 to 12, and mostpreferably 3 to 9 nitrogen atoms in the molecule. These amines may behydrocarbyl amines or may be hydrocarbyl amines including other groups,e.g., hydroxy groups, alkoxy groups, amide groups, nitriles, imidazolinegroups, and the like. Hydroxy amines with 1 to 6 hydroxy groups,preferably 1 to 3 hydroxy groups, are particularly useful. Preferredamines are aliphatic saturated amines, including those of the generalformulas: ##STR17## wherein R⁵, R⁶, R⁷ and R⁸ are independently selectedfrom the group consisting of hydrogen; C₁ to C₂₅ straight or branchedchain alkyl radicals; C₁ to C₁₂ alkoxy; C₂ to C₆ alkylene radicals; C₂to C₁₂ hydroxy amino alkylene radicals; and C₁ to C₁₂ alkylamino C₂ toC₆ alkylene radicals; and wherein R⁸ can additionally comprise a moietyof the formula: ##STR18## wherein R⁶ is as defined above, and wherein rand r' can be the same or a different number of from 2 to 6, preferably2 to 4; and t and t' can be the same or different and are numbers offrom 0 to 10, preferably 2 to 7, and most preferably about 3 to 7.Preferably that the sum of t and t' is not greater than 15. To assure afacile reaction, it is preferred that R⁵, R⁶, R⁷, R⁸, r, r', t and t' beselected in a manner sufficient to provide the compounds of Formula (5)and (6) with typically at least 1 primary or secondary amine group,preferably at least 2 primary or secondary amine groups. This can beachieved by selecting at least 1 of said R⁵, R⁶, R⁷ and R⁸ groups to behydrogen or by letting t in Formula 6 be at least 1 when R⁸ is H or whenthe Formula (7) moiety possesses a secondary amino group. The mostpreferred amine of the above formulas are represented by Formula (6) andcontain at least 2 primary amine groups and at least 1, and preferablyat least 3, secondary amine groups.

Non-limiting examples of suitable amine compounds include:1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; polypropylene aminessuch as 1,2-propylene diamine; di-(1,2-propylene)triamine;di-(1,3-propylene)triamine; N,N-dimethyl-1,3-diaminopropane;N,N-di-(2-aminoethyl) ethylene diamine;N,N-di-(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine;N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);diisopropanol amine; diethanoi amine; triethanol amine; mono-, di-, andtri-tallow amines; amino morpholines such asN-(3-aminopropyl)morpholine; and mixtures thereof. Monoamines includemethyl ethyl amine, methyl octadecyl amines, anilines, diethylol amine,dipropyl amine, etc.

Other useful amine compounds include: alicyclic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula (8): ##STR19## wherein p₁ and p₂ are the same or different andare each integers of from 1 to 4, and n₁, n₂ and n₃ are the same ordifferent and are each integers of from 1 to 3. Non-limiting examples ofsuch amines include 2-pentadecyl imidazoline; N-(2-aminoethyl)piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. Forexample, one process for preparing alkylene amines involves the reactionof an alkylene dihalide (such as ethylene dichloride or propylenedichloride) with ammonia, which results in a complex mixture of alkyleneamines wherein pairs of nitrogens are joined by alkylene groups, formingsuch compounds as diethylene triamine, triethylenetetramine,tetraethylene pentamine and isomeric piperazines. Low costpoly(ethyleneamine) compounds averaging about 5 to 7 nitrogen atoms permolecule are available commercially under trade names such as "PolyamineH", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxyalkylene polyamines such as those ofthe formula:

    NH.sub.2 --alkylene-(--O--alkylene--).sub.m --NH.sub.2     (9)

where m has a value of about 3 to 70 and preferably 10 to 35; and theformula:

    R.sup.9 -(--alkylene-(--O--alkylene--).sub.n --NH.sub.2).sub.a(10)

where n has a value of about 1 to 40 with the provision that the sum ofall the n values is from about 3 to about 70 and preferably from about 6to about 35, and R⁹ is a polyvalent saturated hydrocarbon radical of upto 10 carbon atoms wherein the number of substituents on the R⁹ group isrepresented by the value of "a", which is a number of from 3 to 6. Thealkylene groups in either formula (9) or (10) may be straight orbranched chains containing about 2 to 7, and preferably about 2 to 4carbon atoms.

The polyoxyalkylene polyamines of formulas (9) or (10) above, preferablypolyoxyalkylene diamines and polyoxyalkylene triamines, may have averagemolecular weights ranging from about 200 to about 4,000 and preferablyfrom about 400 to about 2,000. The preferred polyoxyalkylene polyaminesinclude the polyoxyethylene and polyoxypropylene diamines and thepolyoxypropylene triamines having average molecular weights ranging fromabout 200 to 2,000. The polyoxyalkylene polyamines are commerciallyavailable and may be obtained, for example, from the Jefferson ChemicalCompany, Inc. under the trade name "Jeffamines D-230, D-400, D-1000,D-2000, T-403, etc.

A particularly useful class of amines are the polyamido and relatedamines disclosed in U.S. Pat. Nos. 4,857,217; 4,963,275 and 4,956,107,the disclosures of which are herein incorporated by reference, whichcomprise reaction products of a polyamine and an alpha, beta unsaturatedcompound of the formula: ##STR20## wherein X is sulfur or oxygen, Y is--OR¹³, SR¹³, or --NR₁₃ (R¹⁴), and R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are thesame or different and are hydrogen or substituted or unsubstitutedhydrocarbyl. Any polyamine, whether aliphatic, cycloaliphatic, aromatic,heterocyclic, etc., can be employed provided it is capable of addingacross the acrylic double bond and amidifying with, for example, thecarbonyl group (--C(O)--) of the acrylate-type compound of formula (11),or with the thiocarbonyl group (--C(S)--) of the thioacrylate-typecompound of formula (11).

When R¹⁰, R¹¹, R¹², R¹³ or R¹⁴ in Formula (11) are hydrocarbyl, thesegroups can comprise alkyl, cycloalkyl, aryl, alkaryl, aralkyl orheterocyclic, which can be substituted with groups which aresubstantially inert to any component of the reaction mixture underconditions selected for preparation of the amido-amine. Such substituentgroups include hydroxy, halide (e.g., C₁, F₁, I, Br), --SH andalkylthio. When one or more of R¹⁰ through R¹⁴ are alkyl, such alkylgroups can be straight or branched chain, and will generally containfrom 1 to 20, more usually from 1 to 10, and preferably from 1 to 4,carbon atoms. Illustrative of such alkyl groups are methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl,tridecyl, hexadecyl, octadecyl and the like. When one or more of R¹⁰through R¹⁴ are aryl, the aryl group will generally contain from 6 to 10carbon atoms (e.g., phenyl, naphthyl).

For convenience, the following discussion is directed to the preparationand use of amido-amines, although it will be understood that suchdiscussion is also applicable to the thioamido-amines.

The type of amido-amine formed varies with reaction conditions. Forexample, a more linear amido-amine is formed where substantiallyequimolar amounts of the unsaturated carboxylate and polyamine arereacted. The presence of excesses of the ethylenically unsaturatedreactant of formula (11) tends to yield an amido-amine which is morecross-linked than that obtained where substantially equimolar amounts ofreactants are employed. Where, for economic or other reasons, across-linked amido-amine using excess amine is desired, generally amolar excess of the ethylenically unsaturated reactant of about at least10%, such as 10 to 300%, or greater, for example, 25 to 200%, isemployed. For more efficient cross-linking an excess of carboxylatedmaterial should preferably be used since a cleaner reaction ensues. Forexample, a molar excess of about 10 to 100% or greater such as 10 to50%, but preferably an excess of 30 to 50%, of the carboxylatedmaterial. Larger excess can be employed if desired.

In summary, without considering other factors, equimolar amounts ofreactants tend to produce a more linear amido-amine whereas excess ofthe formula (11) reactant tends to yield a more cross-linkedamido-amine. It should be noted that the higher the polyamine (i.e., ingreater the number of amino groups on the molecule) the greater thestatistical probability of cross-linking since, for example, atetraalkylenepentamine, such as tetraethylene pentamine ##STR21## hasmore labile hydrogens than ethylene diamine.

These amido-amine adducts so formed are characterized by both amido andamino groups. In their simplest embodiments they may be represented byunits of the following idealized formula: ##STR22## wherein the R¹⁵ 's,which may be the same or different, are hydrogen or a substituent group,such as a hydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl,etc., and A is a moiety of the polyamine which, for example, may bearyl, cycloalkyl, alkyl, etc., and n4 is an integer such as 1 to 10 orgreater.

The above simplified formula represents a linear amido-amine polymer.However, cross-linked polymers may also be formed by employing certainconditions since the polymer has labile hydrogens which can furtherreact with either the unsaturated moiety by adding across the doublebond or by amidifying with a carboxylate group.

Preferably, however, the amido-amines are not cross-linked to anysubstantial degree, and more preferably are substantially linear.

Preferably, the polyamine reactant contains at least one primary amine,and more preferably from 2 to 4 primary amines, group per molecule, andthe polyamine and the unsaturated reactant of formula (11) are contactedin an amount of from about 1 to 10, more preferably from about 2 to 6,and most preferably from about 3 to 5, equivalents of primary amine inthe polyamine reactant per mole of the unsaturated reactant of formula(11).

As an example of the amido-amine adducts, the reaction of tetraethylenepentaamine (TEPA) with methyl methacrylate can be illustrated asfollows: ##STR23##

The amine compound can be reacted with the functionalized polymer byheating an oil solution containing 5 to 95 wt. % of functionalizedpolymer material to about 100° C. to 200° C., preferably 125° C. to 175°C., generally for 1 to 10, e.g. 2 to 6 hours until the desired amount ofwater is removed. Generally from 0.1 to 1.0, preferably about 0.2 to0.6, e.g. 0.4 to 0.6, moles of functional groups present in thefunctionalized polymer is used, per equivalent of nucleophilic reactant,e.g. amine.

Tris(hydroxymethyl) amino methane (THAM) can be reacted with theaforesaid functionalized polymers to form amides or ester type additivesas taught by U.K. 984,409, or to form oxazoline compounds and boratedoxazoline compounds as described, for example, in U.S. Pat. Nos.4,102,798; 4,116,876 and 4,113,639.

DERIVATIZATION OF POLYMER FROM ALCOHOLS

The functionalized polymers of the present invention can be reacted withalcohols, e.g. to form esters. The alcohols may be aliphatic compoundssuch as monohydric and polyhydric alcohols or aromatic compounds such asphenols and naphthols.

The aromatic hydroxy compounds from which the esters may be derived areillustrated by the following specific examples: phenol, beta-naphthol,alpha-naphthol, cresol, resorcinol, catechol, p,p'di-hydroxybiphenyl,2-chlorophenol, 2,4-dibutylphenol, propene tetramer-substituted phenol,didodecylphenol, 4,4'-methylene-bis-phenol, alpha-decyl-beta-naphthol,polyisobutene (molecular weight of 1000)-substituted phenol, thecondensation product of heptylphenol with 0.5 mole of formaldehyde, thecondensation product of octyl-phenol with acetone,di(hydroxyphenyl)-oxide, di(hydroxyphenyl)sulfide,di(hydroxyphenyl)disulfide, and 4-cyclohexlphenol. Phenol and alkylatedphenols having up to three alkyl substituents are preferred.

The alcohols from which the esters may be derived preferably contain upto about 40 aliphatic carbon atoms. They may be monohydric alcohols suchas methanols, ethanol, isooctanol, dodecanol, cyclohexanol,cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol,isobutyl alcohol, benzyl alcohol, beta-phenyl-ethyl alcohol,2-methylcyclohexanol, beta-chloroethanol, monomethyl ether of ethyleneglycol, monobutyl ether of ethylene glycol, monopropyl ether ofdiethylene glycol, monododecyl ether of triethylene glycol, monooleateof ethylene glycol, monostearate of diethylene glycol, secpentylalcohol, tertbutyl alcohol, 5-bromo-dodecanol, nitro-octadecanol anddioleate of glycerol. The polyhydric alcohols preferably contain from 2to about 10 hydroxy radicals. They are illustrated by, for example,ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, dipropylene glycol, tripropylene glycol, dibutylene glycol,tributylene glycol, and other alkylene glycols in which the alkyleneradical contains from 2 to about 8 carbon atoms. Other useful polyhydricalcohols include glycerol, monooleate of glycerol, monostearate ofglycerol, monomethyl ether of glycerol, pentaerythritol, 9,10-dihydroxystearic acid, methyl ester of 9,10-dihydroxy stearic acid,1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, penacol, erythritol,arabitol, sorbitol, mannitol, 1,2-cyclo-hexanediol, and xylene glycol.Carbohydrates such as sugars, starches, cellulose, etc., likewise mayyield the esters of this invention. The carbohydrates may be exemplifiedby a glucose, fructose, sucrose, rhamnose, mannose, glyceraldehyde, andgalactose. Heterocyclic polyols such as described in U.S. Pat. No.4,797,219, the disclosure of which is herein incorporated by referencemay also be employed. Such polyols includetetrahydro-3,3,5,5-tetrakis(hydroxymethyl)-4-pyranol also known asanhydroennea-heptitol (AEH).

A useful class of polyhydric alcohols are those having at least threehydroxy radicals, some of which have been esterified with amonocarboxylic acid having from about 8 to about 30 carbon atoms, suchas octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoicacid, or tall oil acid. Examples of such partially esterified polyhydricalcohols are the monooleate of sorbitol, distearate of sorbitol,monooleate of glycerol, monostearate of glycerol, di-dodecanoate oferythritol.

The esters may also be derived from unsaturated alcohols such as allylalcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, anoleyl alcohol. Still another class of the alcohols capable of yieldingthe esters of this invention comprise the ether-alcohols andamino-alcohols including, for example, the oxyalkylene-, oxyarylene-,amino-alkylene-, and amino-arylene-substituted alcohols having one ormore oxyalkylene, amino-alkylene or amino-arylene oxyarylene radicals.They are exemplified by Cellosolve, carbitol, phenoxyethanol,heptylphenyl-(oxypropylene) 6-H, octyl-(oxyethylene) 30-H,phenyl-(oxyoctylene)2-H, mono(heptylphenyl-oxypropylene)-substitutedglycerol, poly(styrene oxide), aminoethanol, 3-amino ethyl-pentanol,di(hydroxyethyl) amine, p-amino-phenol, tri(hydroxypropyl)amine,N-hydroxyethyl ethylene diamine, N,N,N',N'-tetrahydroxy-trimethylenediamine, and the like. For the most part, the ether-alcohols having upto about 150 oxyalkylene radicals in which the alkylene radical containsfrom 1 to about 8 carbon atoms are preferred.

The esters may be prepared by one of several methods. The method whichis preferred because of convenience and superior properties of theesters it produces, involves the reaction of a suitable alcohol orphenol with the acid. The esterification is usually carried out at atemperature above about 100° C., preferably between 150° C. and 300° C.

The water formed as a by-product is removed by distillation as theesterification proceeds. A solvent may be used in the esterification tofacilitate mixing and temperature control. It also facilitates theremoval of water from the reaction mixture. The useful solvents includexylene, toluene, diphenyl ether, chlorobenzene, and mineral oil.

The relative proportions of the acid functionalized polymer and thehydroxy reactant which are to be used depend to a large measure upon thetype of the product desired, the functionality of the functionalizedpolymer, and the number of hydroxyl groups present in the molecule ofthe hydroxy reactant.

In some instances, it is advantageous to carry out the esterification inthe presence of a catalyst such as sulfuric acid, pyridinehydrochloride, hydrochloric acid, benzenesulfonic acid,p-toluenesulfonic acid, phosphoric acid, or any other knownesterification catalyst. The amount of the catalyst in the reaction maybe as little as 0.01% (by weight of the reaction mixture), more oftenfrom about 0.1% to about 5%.

Ester derivatives likewise may be obtained by the reaction of a acidfunctionalized polymer with epoxide or a mixture of an epoxide andwater. Such reaction is similar to one involving the acid functionalizedpolymer with a glycol. Epoxides which are commonly available for Use insuch reaction include, for example, ethylene oxide, propylene oxide,styrene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin,cyclohexene oxide, 1,2-octylene oxide, epoxidized soya bean oil, methylester of 9,10-epoxy-stearic acid, and butadiene monoepoxide. Preferredepoxides are the alkylene oxides in which the alkylene radical has from2 to about 8 carbon atoms; or the epoxidized fatty acid esters in whichthe fatty acid radical has up to about 30 carbon atoms and the esterradical is derived from a lower alcohol having up to about 8 carbonatoms.

In lieu of the acid functionalized polymer, a polymer functionalizedwith lactone acid or an acid halide may be used in the processesillustrated above for preparing the ester derivatives of this invention.Such acid halides may be acid bromides and acid chlorides.

In view of the above, the derivative compositions produced by reactingfunctionalized polymer with alcohols are esters including both acidicesters and neutral esters. Acidic esters are those in which less thanall of the functional groups in functionalized polymer are esterified,and hence possess at least one free functional group. Obviously, acidesters are easily prepared by using an amount of alcohol insufficient toesterify all of the functional groups in the functionalized polymer.

The functionalized polymer of this invention is reacted with thealcohols according to conventional esterification, ortransesterification techniques. This normally involves heating thefunctionalized polymer with the alcohol, optionally in the presence of anormally liquid, substantially inert, organic liquid solvent/diluentand/or in the presence of esterification catalyst. Temperatures of atleast about 100° C. up to the decomposition point are used (thedecomposition point having been defined hereinbefore). This temperatureis usually within the range of about 100° C. up to about 300° C. withtemperatures of about 140° C. to 250° C. often being employed.

Many issued patents disclose procedures for reacting high molecularweight carboxylic acids with alcohols to produce acidic esters andneutral esters. These same techniques are applicable to preparing estersfrom the functionalized polymer of this invention and the alcoholsdescribed above. All that is required is that the functionalized polymerof this invention are substituted for the high molecular weightcarboxylic acid acylating agents discussed in these patents, usually onan equivalent weight basis. The following U.S. Pat.s are expresslyincorporated herein by reference for their disclosure of suitablemethods for reacting the acylating reagents of this invention with thealcohols described above: U.S. Pat. Nos. 3,331,776; 3,381,022;3,522,179; 3,542,680; 3,697,428 and 3,755,169.

DERIVATIZED POLYMER FROM REACTIVE METALS/METAL COMPOUNDS

Useful reactive metals or reactive metal compounds are those which willform metal salts of the functionalized polymer or metal-containingcomplexes with the functionalized polymer. Metal complexes are typicallyachieved by reacting the functionalized polymers with amines and/oralcohols as discussed above and also with complex forming reactantseither during or subsequent to amination.

Reactive metal compounds for use in the formation of complexes with thereaction products of functionalized polymer and amines include thosedisclosed in U.S. Pat. No. 3,306,908. Complex-forming metal reactantsinclude the nitrates, nitrites, halides, carboxylates, phosphates,phosphites, sulfates, sulfites, carbonates, borates, and oxides ofcadmium as well as metals having atomic numbers from 24 to 30 (includingchromium, manganese, iron, cobalt, nickel, copper and zinc). Thesemetals are the so-called transition or coordination metals, i.e., theyare capable of forming complexes by means of their secondary orcoordination valence. Specific examples of the complex-forming metalcompounds useful as the metal reactant are copper oxide, copper nitrate,cobaltous nitrate, cobaltous oxide, cobaltic oxide, cobalt nitrite,cobaltic phosphate, cobaltous chloride, cobaltic chloride, cobaltouscarbonate, chromous acetate, chromic acetate, chromic bromide, chromouschloride, chromic fluoride, chromous oxide, chromium dioxide, chromicoxide, chromic sulfite, chromous sulfate heptahydrate, chromic sulfate,chromic formate, chromic hexanoate, chromium oxychloride, chromicphosphite, manganous acetate, manganous benzoate, manganous carbonate,manganese dichloride, manganese trichloride, manganous citrate,manganous formate, manganous nitrate, manganous oxalate, manganesemonooxide, manganese dioxide, manganese trioxide, manganese heptoxide,manganic phosphate, manganous pyrophosphate, manganic metaphosphate,manganous hypophosphite, manganous valerate, ferrous acetate, ferricbenzoate, ferrous bromide, ferrous carbonate, ferric formate, ferrouslactate, ferrous nitrate, ferrous oxide, ferric oxide, ferrichypophosphite, ferric sulfate, ferrous sulfite, ferric hydrosulfite,nickel dibromide, nickel dichloride, nickel nitrate, nickel dioleate,nickel stearate, nickel sulfite, cupric propionate, cupric acetate,cupric metaborate, cupric benzoate, cupric formate, cupric laurate,cupric nitrite; cupric oxychloride, cupric palmitate, cupric salicylate,zinc benzoate, zinc borate, zinc bromide, zinc chromate, zincdichromate, zinc iodide, zinc lactate, zinc nitrate, zinc oxide, zincstearate, zinc sulfite, cadmium benzoate, cadmium carbonate, cadmiumbutyrate, cadmium chloroacetate, cadmium fumarate, cadmium nitrate,cadmium dihydrogenphosphate, cadmium sulfite, and cadmium oxide.Hydrates of the above compounds are especially convenient for use in theprocess of this invention.

U.S. Pat. No. 3,306,908 is expressly incorporated herein by referencefor its discussion of reactive metal compounds suitable for forming suchcomplexes and its disclosure of processes for preparing the complexes.Basically, those processes are applicable to the carboxylic derivativecompositions of the functionalized polymer of this invention with theamines as described above by substituting, or on an equivalent basis,the functionalized polymer of this invention with the high molecularweight carboxylic acid functionalized polymer disclosed in U.S. Pat. No.3,306,908.

U.S. Pat. No. Re. 26,433 discloses metals useful in preparing salts fromacid functionalized polymer and/or an amine derivatized polymer asdescribed hereinabove. Metal salts are prepared, according to thispatent, from alkali metals, alkaline earth metals, zinc, cadmium, lead,cobalt and nickel. Examples of a reactive metal compound suitable foruse are sodium oxide, sodium hydroxide, sodium carbonate, sodiummethylate, sodium propylate, sodium pentylate, sodium phenoxide,potassium oxide, potassium hydroxide, potassium carbonate, potassiummethylate, potassium pentylate, potassium phenoxide, lithium oxide,lithium hydroxide, lithium carbonate, lithium pentylate, calcium oxide,calcium hydroxide, calcium carbonate, calcium methylate, calciumethylate, calcium propylate, calcium chloride, calcium fluoride, calciumpentylate, calcium phenoxide, calcium nitrate, barium oxide, bariumhydroxide, barium carbonate, barium chloride, barium fluoride, bariummethylate, barium propylate, barium pentylate, barium nitrate, magnesiumoxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate,magnesium propylate, magnesium chloride, magnesium bromide, barium,iodide, magnesium phenoxide, zinc oxide, zinc hydroxide, zinc carbonate,zinc methylate, zinc propylate, zinc pentylate, zinc chloride, zincfluoride, zinc nitrate trihydrate, cadmium oxide, cadmium hydroxide,cadmium carbonate, cadmium methylate, cadmium propylate, cadmiumchloride, cadmium bromide, cadmium fluoride, lead oxide, lead hydroxide,lead carbonate, lead ethylate, lead pentylate, lead chloride, leadfluoride, lead iodide, lead nitrate, nickel oxide, nickel hydroxide,nickel carbonate, nickel chloride, nickel bromide, nickel fluoride,nickel methylate, nickel pentylate, nickel nitrate hexahydrate, cobaltoxide, cobalt hydroxide, cobaltous bromide, cobaltous chloride, cobaltbutylate, cobaltous nitrate hexahydrate, etc. The above metal compoundsare merely illustrative of those useful in this invention and theinvention is not to be considered as limited to such.

U.S. Pat. No. Re. 26,433 is expressly incorporated herein by referencefor its disclosure of useful reactive metal compounds as, and processesfor, utilizing these compounds in the formation of salts. Again, inapplying the teachings of this patent to the present invention, it isonly necessary to substitute the functionalized polymer of thisinvention on an equivalent weight basis for the high molecular weightcarboxylic acylating agents disclosed in this reissue patent.

U.S. Pat. No. 3,271,310 is expressly incorporated herein by referencefor its disclosure of suitable reactive metal compounds suitable forforming salts of functionalized polymer as well as illustrativeprocesses for preparing salts of these reagents. As will be apparent,the processes of U.S. Pat. No. 3,271,310 are applicable to thisinvention merely by substituting on an equivalent weight basis, thefunctionalized polymer of this invention for the high molecular weightcarboxylic acids of the patent.

Derivatization Reactant Ratios

From the foregoing description, it is apparent that the appropriatefunctionalized polymer of this invention can be reacted with anyindividual derivatizing compound such as amine, alcohol, reactive metal,reactive metal compound or any combination of two or more of any ofthese; that is, for example, one or more amines, one or more alcohols,one or more reactive metals or reactive metal compounds, or a mixture ofany of these. The mixture can be a mixture of two or more amines, amixture of two or more alcohols, a mixture of two or more metals orreactive metal compounds, or a mixture of two or more componentsselected from amines and alcohols, from amines and reactive metals orreactive metal compounds, from alcohols and reactive metal compounds, orone or more components from each of the amines, alcohols, and reactivemetals or reactive metal compounds. Furthermore, the appropriatefunctionalized polymer of this invention can be reacted with the amines,alcohols, reactive metals, reactive metal compounds, or mixturesthereof, as described above, simultaneously (concurrently) orsequentially in any order of reaction.

In any of the foregoing derivatizing reactions involving the use of thefunctionalized polymer of this invention, substantially inert organicliquid diluents may be used to facilitate mixing, temperature control,and handling of the reaction mixture. Suitable diluents includealiphatic, cycloaliphatic, and aromatic hydrocarbons as well as thecorresponding halogenated hydrocarbons, particularly chlorinatedhydrocarbons. These diluents are exemplified by benzene, toluene,xylene, chlorobenzenes, hexane, heptane, cyclohexane, or mixtures ofthese. Mineral oils particularly low viscosity mineral oils are verygood diluents. Other organic solvents can also be employed such asethers, sulfoxide, sulfones, and the like. Where one or more of thereactants themselves are liquid at the reaction temperature, thereactant itself functions as a diluent and it may be convenientsometimes to employ an excess amount of the reactant to serve thispurpose.

The following discussion is intended to explain and illustrate what ismeant by the term "equivalent" with respect to various classes ofreactants as the term is used herein. As will be shown a "derivatizationratio" defined as the molar equivalent ratios of the functionalizedpolymer to derivatizing compound.

The number of equivalents which characterize the functionalized polymerof the invention depends upon the number of functional groups presentwithin the structure thereof as expressed by its functionality (F or Nof Formula I).

Thus, a functionalized polymer having a functionality of 3 has anaverage of three equivalents per mole. Alternatively, 6,000 Mn polymerfunctionalized with acid to a functionality of 3 possesses an equivalentweight of 2000 per mole.

A nitrogen-containing derivatizing compound such as an amine reactant,is regarded as having a number of equivalents per mole corresponding tothe average number of reactive amine groups, i.e., primary or secondaryamine groups, per molecule. Thus, ammonia has one equivalent per mole;urea, hydrazine, ethylenediamine, and piperazine have two equivalentsper mole; and tetraethylene pentamine has five equivalents per mole.Mixtures of nitrogen-containing reactants such as mixtures of alkylenepolyamines are regarded as having an equivalent weight equal to theweight of the mixture divided by the number of reactive nitrogen atomspresent. For example, 1,000 parts of a polyethylene polyamine mixturecontaining 37 percent by weight nitrogen has an equivalent weight ofabout 38.

In like manner, hydroxyaromatic compounds and alcohols have equivalentweights equal to their molecular weights divided by the number offunctional --OH groups per molecule. Or, from another viewpoint, theypossess a number of equivalents per mole equal to the number of --OHgroups. Thus, pentaerythritol has four equivalents per mole and anequivalent weight of 34. Phenol has one equivalent per mole so that itsequivalent weight equals its molecular weight.

Metal reactants have an equivalent weight equal to their molecularweight divided by the product of the number of metal atoms per moleculeof reactant times the valence of the metal. Since most of the metalreactants have only one metal per atom per molecule, the equivalentweight of the metal reactant is normally the molecular weight divided bythe valence of the metal. Stated differently, a metal reactant normallyhas a number of equivalents per mole equal to the valence of the metal.For example, calcium hydroxide, zinc chloride, and barium oxide have twoequivalents per mole; sodium hydroxide and lithium hydroxide have oneequivalent per mole.

From what has been said hereinabove, it will be apparent to thoseskilled in the art that the reaction products produced by reactingfunctionalized polymer of this invention with derivatizing compoundssuch as alcohols, nitrogen-containing reactants, metal reactants, andthe like will, in fact, be mixtures of various reaction products. Thisis especially apparent in view of the fact that the functionalizedpolymers themselves can be mixtures of materials. For example, if acidfunctionalized polymer is reacted with a polyol, the esterificationproduct can contain esters wherein only one hydroxyl group has beenesterified, esters wherein two or more of the hydroxy groups have beenesterified by the same or different functionalized polymer, esters whereall of the carboxyl groups of an acid functionalized polymer have beenesterified, esters where less than all of the carboxyl groups offunctionalized polymer have been esterified, and the like. However, forpurposes of the present invention it is not necessary to know thespecific structure of each derivatized component of the reactionmixtures produced, since it is not necessary to isolate these componentsin order to use them as additives, e.g., in lubricants and fuels.

While the functionalized polymers themselves possess some dispersantcharacteristics and can be used as dispersant additives in lubricantsand fuels, best results are achieved when at least about 30, preferably,at least about 50, most preferably 100% of the functional groups arederivatized. Furthermore, it is not necessary that all the functionalgroups of the functionalized polymer be derivatized to the same productor even the same type of product. Thus, functionalized polymer may befirst reacted with one or more alcohols to convert a portion of acidfunctional groups to ester groups and thereafter this ester product canbe reacted with one or more amines and/or one or more metal reactants toconvert all or a portion of the remaining carboxyl functions to aderivatized amine groups such as amides, imides, amidines, amine saltgroups, and the like or metal salt groups.

In view of the above, the "derivatization ratio" can vary considerably,depending, e.g., on the reactants and type of bonds sought to be formed.Thus, while any derivatization ratio effective to impart the desiredproperties to the derivatized polymer can be employed, it iscontemplated that such effective ratios will range typically from about0.05:1 to about 4:1, preferably 0.5:1 to about 2.0:1 (e.g. 0.6:1 toabout 1.5:1) and most preferably 0.7:1 to about 1:1 (e.g. 0.8:1 to0.9:1). As can be seen from the above ratios it is preferred to employan excess of derivatizing compound from an equivalents standpoint,particularly where the unreacted excess thereof can be easily strippedfrom the reaction mixture.

Post Treatment

Another aspect of this invention involves the post treatment ofderivatized polymer. The processes for post-treating derivatized polymerare analogous to the post-treating processes used with respect toconventional dispersants and MFVI's of the prior art. Accordingly, thesame reaction conditions, ratio of reactants and the like can be used.Reference is made to U.S. Pat. No. 5,017,199.

Accordingly, derivatized polymer can be post-treated with such reagentsas urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylicacids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides,boron compounds, phosphorus compounds or the like. Exemplary materialsof this kind are described in the following U.S. Pat. Nos. 3,036,003;3,200,107; 3,254,025; 3,278,550; 3,281,428; 3,282,955; 3,366,569;3,373,111; 3,442,808; 3,455,832; 3,493,520; 3,513,093; 3,539,633;3,579,450; 3,600,372; 3,639,242; 3,649,659; 3,703,536 and 3,708,522which are herein incorporated by reference.

The amine derivatized polymers of the present invention as describedabove can be post-treated, particularly for use as dispersants andviscosity index improvers by contacting said polymers with one or morepost-treating reagents selected from the group consisting of boronoxide, boron oxide hydrate, boron halides, boron acids, esters of boronacids, carbon disulfide, sulfur, sulfur chlorides, alkenyl cyanides,aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide,hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbylthiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides,phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates,hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides,episulfides, formaldehyde or formaldehyde-producing compounds plusphenols, and sulfur plus phenols, and C₁ to C₃₀ hydrocarbyl substitutedsuccinic acids and anhydrides (e.g., succinic anhydride, dodecylsuccinic anhydride and the like), fumaric acid, itaconic acid, maleicacid, maleic anhydride, chloromaleic acid, chloromaleic anhydride,acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and loweralkyl (e.g., C₁ to C₄ alkyl) acid esters of the foregoing, e.g., methylmaleate, ethyl fumarate, methyl fumarate, and the like.

For example, the amine derivatized polymers can be treated with a boroncompound selected from the class consisting of boron oxide, boronhalides, boron acids and esters of boron acids in an amount to providefrom about 0.1 atomic proportion of boron for each mole of said nitrogencomposition to about 20 atomic proportions of boron for each atomicproportion of nitrogen of said nitrogen composition. Borated derivatizedpolymer useful as dispersants can contain from about 0.05 to 2.0 wt. %,e.g. 0.05 to 0.7 wt. % boron based on the total weight of said boratednitrogen-containing dispersant compound. The boron, which appears to bein the product as dehydrated boric acid polymers (primarily (HBO₂)₃), isbelieved to attach to the derivatized polymer as amine salts, e.g., themetaborate salt of said amine derivatized polymers. Treating is readilycarried out by adding from about 0.05 to 4, e.g. 1 to 3 wt. % (based onthe weight of said derivatized polymer) of said boron compound,preferably boric acid which is most usually added as a slurry to saidnitrogen compound and heating with stirring at from about 135° C. to190° C., e.g. 140° C. to 170° C., for from 1 to 5 hours followed bynitrogen stripping at said temperature ranges.

Since post-treating processes involving the use of these post-treatingreagents is known insofar as application to high molecular weightnitrogen-containing dispersants of the prior art, further descriptionsof these processes herein is unnecessary. In order to apply the priorart processes to the compositions of this invention, all that isnecessary is that reaction conditions, ratio of reactants, and the likeas described in the prior art, be applied to the novel compositions ofthis invention. The following U.S. patents are expressly incorporatedherein by reference for their disclosure of post-treating processes andpost-treating reagents applicable to the compositions of this invention:U.S. Pat. Nos. 3,087,936; 3,200,107; 3,254,025; 3,256,185; 3,278,550;3,281,428; 3,282,955; 3,284,410; 3,338,832; 3,344,069; 3,366,569;3,373,111; 3,367,943; 3,403,102; 3,428,561; 3,502,677; 3,513,093;3,533,945; 3,541,012; 3,639,242; 3,708,522; 3,859,318; 3,865,813;3,470,098; 3,369,021; 3,184,411; 3,185,645; 3,245,908; 3,245,909;3,245,910; 3,573,205; 3,692,681; 3,749,695; 3,865,740; 3,954,639;3,458,530; 3,390,086; 3,367,943; 3,185,704; 3,551,466; 3,415,750;3,312,619; 3,280,034; 3,718,663; 3,652,616; UK Patent No. 1,085,903; UKPatent No. 1,162,436; U.S. Pat. No. 3,558,743. Particularly preferredfor post-treating is the process disclosed in commonly assigned U.S.Ser. No. 992,413, filed Dec. 17, 1992 entitled Improved Low SedimentProcess for Forming Borated Dispersant, Docket No. PT-849.

The derivatized polymers of the present invention can also be treatedwith polymerizable lactones (such as epsilon-caprolactone) to formdispersant adducts having the moiety --[C(O)(C₂)_(z) O]_(m) H, wherein zis a number of from 4 to 8 (e.g., 5 to 7) and m has an average value offrom about 0 to 100 (e.g., 0.2 to 20). The derivatized polymers of thisinvention, particularly for use as a dispersant, can be post-treatedwith a C₅ to C₉ lactone, e.g., epsilon-caprolactone, by heating amixture of the polymers and lactone in a reaction vessel in the absenceof a solvent at a temperature of about 50° C. to about 200° C., morepreferably from about 75° C. to about 180° C., and most preferably fromabout 90° C. to about 160° C., for a sufficient period of time to effectreaction. Optionally, a solvent for the lactone, dispersant materialand/or the resulting adduct may be employed to control viscosity and/orthe reaction rates.

In one preferred embodiment, the C₅ to C₉ lactone, e.g.,epsilon-caprolactone, is reacted with a nitrogen containing polymer(i.e., dispersant) in a 1:1 mole ratio of lactone to dispersantmaterial. In practice, the ratio of lactone to polymer may varyconsiderably as a means of controlling the length of the sequence of thelactone units in the adduct. For example, the mole ratio of the lactoneto the dispersant material may vary from about 10:1 to about 0.1:1, morepreferably from about 5:1 to about 0.2:1, and most preferably from about2:1 to about 0.4:1. It is preferable to maintain the average degree ofpolymerization of the lactone monomer below about 00, with a degree ofpolymerization on the order of from about 0.2 to about 50 beingpreferred, and from about 0.2 to about 20 being more preferred. Foroptimum dispersant performance the nitrogen containing polymer as adispersant, sequences of from about 1 to about 5 lactone units in a roware preferred.

Catalysts useful in the promotion of the lactone-post-treatmentreactions are selected from the group consisting of stannous octanoate,stannous hexanoate, tetrabutyl titanate, a variety of organic-based acidcatalysts and amine catalysts, as described on page 266, and forward, ina book chapter authored by R. D. Lundberg and E. F. Cox, entitled"Kinetics and Mechanisms of Polymerization: Ring OpeningPolymerization", edited by Frisch and Reegen, published by Marcel Dekkerin 1969, wherein stannous octanoate is an especially preferred catalyst.The catalyst is added to the reaction mixture at a concentration levelof about 50 to about 10,000 parts per weight of catalyst per one millionparts of the total reaction mixture.

The reactions of such lactones with dispersant materials containingnitrogen or ester groups is more completely described in U.S. Pat. Nos.4,906,394; 4,866,141; 4,866,135; 4,866,140; 4,866,142; 4,866,139 and4,963,275, the disclosure of each of which is hereby incorporated byreference in its entirety.

Lubricating Compositions

The above discussions relate to a variety of materials including theKoch functionalized polymer, the derivatized polymer, and post-treatedderivatized polymer.

The Koch functionalized polymer, in addition to acting as intermediatesfor dispersant and MFVI manufacture, can be used as molding releaseagents, molding agents, metal working lubricants, point thickeners andthe like.

The primary utility for all the above-described material, fromfunctionalized polymer all the way through post-treated derivatizedpolymer, is as and additive for oleaginous compositions. For ease ofdiscussion the above-mentioned materials are collectively andindividually referred to herein as additives when used in the context ofan oleaginous composition containing such "additives".

Accordingly, the additives of the present invention may be used byincorporation and dissolution into an oleaginous material such as fuelsand lubricating oils. When the additives of this invention are used innormally liquid petroleum fuels such as middle distillates boiling fromabout 65° C. to 430° C., including kerosene, diesel fuels, home heatingfuel oil, jet fuels, etc., a concentration of the additives in the fuelin the range of typically from about 0.001 to about 0.5, and preferably0.005 to about 0.15 wt. %, based on the total weight of the composition,will usually be employed.

The additives of the present invention find their primary utility inlubricating oil compositions which employ a base oil in which theadditives are dissolved or dispersed therein. Such base oils may benatural or synthetic. Base oils suitable for use in preparing thelubricating oil compositions of the present invention include thoseconventionally employed as crankcase lubricating oils for spark-ignitedand compression-ignited internal combustion engines, such as automobileand truck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing the additivemixtures of the present invention in base oils conventionally employedin and/or adapted for use as power transmitting fluids, universaltractor fluids and hydraulic fluids, heavy duty hydraulic fluids, powersteering fluids and the like. Gear lubricants, industrial oils, pumpoils and other lubricating oil compositions can also benefit from theincorporation therein of the additives of the present invention.

These lubricating oil formulations conventionally contain severaldifferent types of additives that will supply the characteristics thatare required in the formulations. Among these types of additives areincluded viscosity index improvers, antioxidants, corrosion inhibitors,detergents, dispersants, pour point depressants, antiwear agents,friction modifiers, etc.

The additives of the present invention, particularly those adapted foruse as dispersants or viscosity modifiers, can be incorporated into alubricating oil in any convenient way. Thus, they can be added directlyto the oil by dispersing or dissolving the same in the oil at thedesired level of concentrations of the additive. Such blending into theadditional lube oil can occur at room temperature or elevatedtemperatures. Alternatively, the additives can be blended with asuitable oil-soluble solvent and base oil to form a concentrate, andthen blending the concentrate with a lubricating oil basestock to obtainthe final formulation. Such dispersant concentrates will typicallycontain (on an active ingredient (AI) basis) from about 10 to about 80wt. %, typically about 20 to about 60 wt. %, and preferably from about40 to about 50 wt. %, additive, and typically from about 40 to 80 wt. %,preferably from about 40 to 60 wt. %, base oil, i.e., hydrocarbon oilbased on the concentrate weight. MFVI concentrates typically willcontain from about 5 to about 50 wt. % AI.

The lubricating oil basestock for the additive typically is adapted toperform a selected function by the incorporation of additional additivestherein to form lubricating oil compositions (i.e., formulations).

Usually these concentrates may be diluted with 3 to 100, e.g., 5 to 40parts by weight of lubricating oil, per part by weight of the additivepackage, in forming finished lubricants, e.g. crankcase motor oils. Thepurpose of concentrates, of course, is to make the handling of thevarious materials less difficult and awkward as well as to facilitatesolution or dispersion in the final blend. Thus, the additives of thepresent invention and formulations containing them would usually beemployed in the form of a 40 to 50 wt. % concentrate, for example, in alubricating oil fraction.

The additives of the present invention will be generally used inadmixture with a lube oil basestock, comprising an oil of lubricatingviscosity, including natural and synthetic lubricating oils and mixturesthereof. Useful oils are described in U.S. Pat. Nos. 5,017,299 and5,084,197.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halosubstitutedhydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,polybutylenes, polypropylenes, propylene-isobutylene copolymers,chlorinated polybutylenes, etc.) poly(hexenes), poly(1-octenes),poly(1-decenes), etc. and mixtures thereof; alkylbenzenes (e.g.,dodecyl-benzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated diphenyl ethers and alkylated diphenyl sulfidesand the derivatives, analogs and homologs thereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known syntheticlubricating oils. These are exemplified by polyoxyalkylene polymersprepared by polymerization of ethylene oxide or propylene oxide, thealkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methylpoly isopropylene glycol ether having an average molecular weightof 1000, diphenyl ether of polyethylene glycol having a molecular weightof 500 to 1,000, diethyl ether of polypropylene glycol having amolecular weight of 1,000 to 1,500; and mono- and polycarboxylic estersthereof, for example, the acetic acid esters, mixed C₃ to C₈ fatty acidesters and C₁₃ Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalatedidecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, and the complex ester formed by reacting 1 mole ofsebacic acid with 2 moles of tetraethylene glycol and 2 moles of2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol andtripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxysiloxane oils and silicate oils comprise another useful classof synthetic lubricants; they include tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-2-ethylhexyl)silicate,tetra-(p-tert-butylphenyl)silicate, hexa-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Othersynthetic lubricating oils include liquid esters ofphosphorus-containing acids (e.g., tricresyl phosphate, trioctylphosphate, diethyl ester of decylphosphonic acid) and polymerictetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment. Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to thoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.

Additional Formulation Components

As indicated above, the additives of the present invention may be mixedwith other types of additives selected to perform at least one desiredfunction. Typical of such formations are detergent/inhibitor, viscositymodification, wear inhibitor, oxidation inhibitor, corrosion inhibitor,friction modifier, foam inhibitor, rust inhibitor, demulsifier, lube oilflow improvers, and seal swell control. Each class of such additionaladditions is discussed in more detail below.

Detergent/Inhibitor

Metal-containing detergents which can also act as rust inhibitors hencethe term "detergent/inhibitor" or simply "DI", include the metal saltsof sulphonic acids, alkyl phenols, sulphurized alkyl phenols, alkylsalicylates, naphthenates, and other oil soluble mono- and dicarboxylicacids as well as metal-containing complexes thereof. Usually thesemetal-containing detergent/inhibitors are used in lubricating oil inamounts of about 0.01 to 10, e.g. 0.1 to 5 wt. %, based on the weight ofthe total lubricating composition-Marine diesel lubricating oilstypically employ such metal-containing rust inhibitors and detergents inamounts of up to about 20 wt. %.

Metal detergent/inhibitors are generally basic (viz, overbased) alkalior alkaline earth metal salts (or mixtures thereof, e.g. mixtures of Caand Mg salts) of one or more organic sulfonic acid (generally apetroleum sulfonic acid or a synthetically prepared alkaryl sulfonicacid), petroleum naphthenic acids, alkyl benzene sulfonic acids, alkylphenols, alkylene-bis-phenols, oil soluble fatty acids and the like,such as are described in U.S. Pat. Nos. 2,501,731; 2,616,904; 2,616,905;2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,777,874;3,027,325; 3,256,186; 3,282,835; 3,384,585; 3,373,108; 3,350,308;3,365,396; 3,342,733; 3,320,162; 3,312,618; 3,318,809 and 3,562,159, thedisclosures of which are herein incorporated by reference. Among thepetroleum sulfonates, the most useful products are those prepared by thesulfonation of suitable petroleum fractions with subsequent removal ofacid sludge and purification. Synthetic alkaryl sulfonic acids areusually prepared from alkylated benzenes such as the Friedel-Craftsreaction product of benzene and a polymer such as tetrapropylene, C₁₈ toC₂₄ hydrocarbon polymer, etc. Suitable acids may also be obtained bysulfonation of alkylated derivatives of such compounds as diphenyleneoxide thianthrene, phenolthioxine, diphenylene sulfide, phenothiazine,diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, decahydronaphthalene and the like.

The terms "basic salt" and "overbased salt" are used to designate metalsalts wherein the metal is present in stoichiometrically larger amountsthan the acid radical.

As used in this discussion, the term "complex" refers to basic metalsalts which contain metal in an amount in excess of that present in aneutral or normal metal salt. The "base number" of a complex is thenumber of milligrams of KOH to which one gram of the complex isequivalent as measured by titration.

The commonly employed methods for preparing the basic salts involveheating a mineral oil solution of the normal metal salt of the acid witha metal neutralizing agent. The use of a "promoter" in theneutralization step to aid the incorporation of a large excess of metalis known and is preferred for the preparation of such compositions.

Examples of compounds useful as the promoter include phenolic substancessuch as phenol, naphthol, alkyl phenols, thiophenol, sulfurized alkylphenols, and condensation products of formaldehyde with a phenolicsubstance; alcohols such as methanol, 2-propanol, octanol, cellosolve,carbitol, ethylene glycol, stearyl alcohol and cyclohexanol; and aminessuch as aniline, phenylene diamine, phenothiazine, phenolbeta-naphthylamine and dodecylamine.

The alkali and alkaline earth metal compounds which may be used inneutralizing these acids to provide the metal salts include the oxidesand hydroxides, alkoxides, carbonates, carboxylate, sulfide,hydrosulfide, nitrate, borates and ethers of magnesium, calcium, andbarium. Examples are calcium oxide, calcium hydroxide, magnesium acetateand magnesium borate. As noted, the alkaline earth metal compound isused in excess of that required to complete neutralization of thealkaryl sulfonic acids. Generally, the amount ranges from about 100 to220%, although it is preferred to use at least 125%, of thestoichiometric amount of metal required for complete neutralization.

Various other preparations of basic alkaline earth metal alkarylsulfonates are known, such as U.S. Pat. Nos. 3,150,088 and 3,150,089wherein overbasing is accomplished by hydrolysis of analkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbonsolvent-diluent oil.

An example of a convenient process for the preparation of themetal-containing complexes employs an oil-soluble sulfonic acid, such asa synthetically prepared didodecylbenzene sulfonic acid, which is mixedwith an excess of lime (e.g., 10 equivalents per equivalent of the acid)and a promoter such as methanol, heptylphenol, or mixture thereof, and asolvent such as mineral oil, at 50° C. to 150° C. and the process massis then carbonated until a homogeneous mass is obtained. Complexes ofsulfonic acids, carboxylic acids, and mixtures thereof are obtainable byprocesses such as are described in U.S. Pat. No. 3,312,618. Anotherexample is the preparation of a magnesium sulfonate normal magnesiumsalt thereof, an excess of magnesium oxide, water, and preferably alsoan alcohol such as methanol.

The carboxylic acids useful for preparing sulfonate carboxylatecomplexes, and carboxylate complexes, i.e., those obtainable fromprocesses such as the above wherein a mixture of sulfonic acid andcarboxylic acid or a carboxylic acid alone is used in lieu of thesulfonic acid, are oil-soluble acids and include primarily fatty acidswhich have at least about 12 aliphatic carbon atoms and not more thanabout 24 aliphatic carbon atoms. Examples of these acids include:palmitic, stearic, myristic, oleic, linoleic, dodecanoic, behenic, etc.Cyclic carboxylic acids may also be employed. These include aromatic andcycloaliphatic acids. The aromatic acids are those containing abenzenoid structure (i.e., benzene, naphthalene, etc.) and anoil-solubilizing radical or radicals having a total of at least about 15to 18 carbon atoms, preferably from about 15 to about 200 carbon atoms.Examples of the aromatic acids include: stearyl-benzoic acid, phenylstearic acid, mono- or polywax-substituted benzoic or naphthoic acidswherein the wax group consists of at least about 18 carbon atoms, cetylhydroxybenzoic acids, etc. The cycloaliphatic acids contemplated have atleast about 12, usually up to about 30 carbon atoms. Examples of suchacids are petroleum naphthenic acids, cetyl cyclohexane carboxylicacids, dilauryl decahydro naphthalene carboxylic acids, dioctylcyclopentane carboxylic acids, etc. The thiocarboxylic acid analogs ofthe above acids, wherein one or both of the oxygen atoms of the carboxylgroup are replaced by sulfur, are also contemplated.

The ratio of the sulfonic acid to the carboxylic acid in mixtures istypically at least 1:1 (on a chemical equivalent basis) and is usuallyless than 5:1, preferably from 1:1 to 2:1.

Usually, the basic composition obtained according to the above-describedmethod is treated with carbon dioxide until its total base number (TBN)is less than about 50, as determined by ASTM procedure D-2896. In manyinstances, it is advantageous to form the basic product by adding a Caor Mg base portionwise and carbonating after the addition of eachportion. Products with very high metal ratios (10 or above) can beobtained by this method. As used herein, the term "metal ratio" refersto the ratio of total equivalents of alkaline earth metal in thesulfonate complex to equivalents of sulfonic acid anion therein. Forexample, a normal sulfonate has a metal ratio of 1.0 and a calciumsulfonate complex containing twice as much calcium as the normal salthas a metal ratio of 2.0. The overbased metal detergent compositionsusually have metal ratios of at least about 1.1, for example, from about1.1 to about 30, with metal ratios of from about 2 to 20 beingpreferred.

Neutral metal sulfonates are frequently used as rust inhibitors.Polyvalent metal alkyl salicylate, naphthenate and phenate materials areknown additives for lubricating oil compositions to improve their hightemperature performance and to counteract deposition of carbonaceousmatter on pistons (U.S. Pat. No. 2,744,069). They can be methylenebridged or sulfur bridged.

The sulfurized metal phenates represent a preferred class of phenatesand can be considered the "metal salt of a phenol sulfide" which thusrefers to a metal salt whether neutral or basic. They can be typified bythe general formula: ##STR24## where x=1 or 2, n=0, 1 or 2; or apolymeric form of such a compound, where R is an alkyl radical, n and xare each integers from 1 to 4, and the average number of carbon atoms inall of the R groups is at least about 9 in order to ensure adequatesolubility in oil. The individual R groups may each contain from 5 to40, preferably 8 to 20, carbon atoms. The metal salt is prepared byreacting an alkyl phenol sulfide with a sufficient quantity of metalcontaining material to impart the desired alkalinity to the sulfurizedmetal phenate.

Regardless of the manner in which they are prepared, the sulfurizedalkyl phenols which are useful generally contain from about 2 to about14 wt. %, preferably about 4 to about 12 wt. % sulfur based on theweight of sulfurized alkyl phenol.

The sulfurized alkyl phenol may also be converted by reaction with ametal containing material including oxides, hydroxides and complexes inan amount sufficient to neutralize said phenol and, if desired, tooverbase the product to a desired alkalinity by procedures well known inthe art. Preferred is a process of neutralization utilizing a solutionof metal in a glycol ether.

The neutral or normal sulfurized metal phenates are those in which theratio of metal to phenol nucleus is about 1:2. The "overbased" or"basic" sulfurized metal phenates are sulfurized metal phenates whereinthe ratio of metal to phenol is greater than that of stoichiometric,e.g. basic sulfurized metal dodecyl phenate, has a metal content up toand greater than 100% in excess of the metal present in thecorresponding normal sulfurized metal phenates wherein the excess metalis produced in oil-soluble or dispersible form (as by reaction withCO₂).

Magnesium and calcium containing detergents although beneficial in otherrespects can increase the tendency of the lubricating oil to oxidize.This is especially true of the highly basic sulphonates.

The magnesium and/or calcium is generally present as basic or neutraldetergents such as the sulphonates and phenates.

Viscosity Modifiers

A viscosity index (V.I.) improver, also referred to as viscositymodifier, is typically employed in multi-grade automobile enginelubricating oils. Viscosity modifiers impart high and low temperatureoperability to the lubricating oil and permit it to remain relativelyviscous at elevated temperatures and also exhibit acceptable viscosityor fluidity at low temperatures. Viscosity modifiers are generally highmolecular weight hydrocarbon polymers including polyesters. Theviscosity modifiers may include derivatized polymers recited above whichinclude various properties or functions, including dispersancyproperties. These oil soluble viscosity modifying polymers willgenerally have number average molecular weights of from 10³ to 10⁶,preferably 10⁴ to 10⁶, e.g., 20,000 to 250,000, as determined by gelpermeation chromatography or osmometry.

Examples of suitable hydrocarbon polymers which can be used areviscosity improvers include homopolymers and copolymers of two or moremonomers of C₂ to C₃₀, e.g. C₂ to C₈ olefins, including both alphaolefins and internal olefins, which may be straight or branched,aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc. Frequentlythey will be of ethylene with C₃ to C₃₀ olefins, particularly preferredbeing the copolymers of ethylene and propylene. Other polymers can beused such as polyisobutylenes, homopolymers and copolymers of C₆ andhigher alpha olefins, atactic polypropylene, hydrogenated polymers andcopolymers and terpolymers of styrene, e.g. with isoprene and/orbutadiene and hydrogenated derivatives thereof. The polymer may bedegraded in molecular weight, for example, by mastication, extrusion,oxidation or thermal degradation, and it may be oxidized and containoxygen. Also included are derivatized polymers such as post-graftedinterpolymers of ethylene-propylene with an active monomer such asmaleic anhydride which may be further reacted with an alcohol, or amine,e.g. an alkylene polyamine or hydroxy amine, e.g., see U.S. Pat. Nos.4,089,794: 4,160,739 and 4,137,185; or copolymers of ethylene andpropylene reacted or grafted with nitrogen compounds such as shown inU.S. Pat. Nos. 4,068,056; 4,068,058; 4,146,489 and 4,149,984.

Useful hydrocarbon polymers include ethylene copolymers containing from15 to 90 wt. % ethylene, preferably 30 to 80 wt. % of ethylene and 10 to85 wt. %, preferably 20 to 70 wt. % of one or more C₃ to C₂₈, preferablyC₃ to C₁₈, more preferably C₃ to C₈, alpha-olefins. While not essential,such copolymers preferably have a degree of crystallinity of less than25 wt. %, as determined by X-ray and differential scanning calorimetry.Copolymers of ethylene and propylene or ethylene and butene are mostpreferred. Other alpha-olefins suitable in place of propylene to formthe copolymer, or to be used in combination with ethylene and propylene,to form a terpolymer, tetrapolymer, etc., include 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc.; also branchedchain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene,5-methylpentene-1,4,4-dimethyl-1-pentene, and 6-methylheptene-1, etc.,and mixtures thereof.

Terpolymers, tetrapolymers, etc., of ethylene, said C₃ to C₂₈alpha-olefin, and a non-conjugated diolefin or mixtures of suchdiolefins may also be used. The amount of the non-conjugated diolefingenerally ranges from about 0.5 to 20 mole %, preferably from about 1 toabout 7 mole %, based on the total amount of ethylene and alpha-olefinpresent.

The polyester V.I. improvers are generally polymers of esters ofethylenically unsaturated C₃ to C₈ mono- and dicarboxylic acids such asmethacrylic and acrylic acids, maleic acid, maleic anhydride, fumaricacid, etc.

Examples of unsaturated esters that may be used include those ofaliphatic saturated mono alcohols of at least 1 carbon atom andpreferably of from 12 to 20 carbon atoms, such as decyl acrylate, laurylacrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate,decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetylmethacrylate, stearyl methacrylate, and the like and mixtures thereof.

Other esters include the vinyl alcohol esters of C₂ to C₂₂ fatty or monocarboxylic acids, preferably saturated such as vinyl acetate, vinyllaurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like andmixtures thereof. Copolymers of vinyl alcohol esters with unsaturatedacid esters such as the copolymer of vinyl acetate with dialkylfumarates, can also be used.

The esters may be copolymerized with still other unsaturated monomerssuch as olefins, e.g. 0.2 to 5 moles of C₂ to C₂₀ aliphatic or aromaticolefin per mole of unsaturated ester, or per mole of unsaturated acid oranhydride followed by esterification. For example, copolymers or styrenewith maleic anhydride esterified with alcohols and amines are known,e.g., see U.S. Pat. No. 3,702,300.

Such ester polymers may be grafted with, or the ester copolymerizedwith, polymerizable unsaturated nitrogen-containing monomers to impartdispersancy to the V.I. improvers. Examples of suitable unsaturatednitrogen-containing monomers include those containing 4 to 20 carbonatoms such as amino substituted olefins asp-(beta-diethylaminoethyl)styrene; basic nitrogen-containingheterocycles carrying a polymerizable ethylenically unsaturatedsubstituent, e.g. the vinyl pyridines and the vinyl alkyl pyridines suchas 2-vinyl-5-ethyl pyridine, 2-methyl-5-vinyl pyridine,2-vinyl-pyridine, 4-vinylpyridine, 3-vinyl-pyridine,3-methyl-5-vinyl-pyridine, 4-methyl-2-vinyl-pyridine,4-ethyl-2-vinyl-pyridine and 2-butyl-1-5-vinyl-pyridine and the like.N-vinyl lactams are also suitable, e.g. N-vinyl pyrrolidones or N-vinylpiperidones. The vinyl pyrrolidones are preferred and are exemplified byN-vinyl pyrrolidone, N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone, N-vinyl-5-ethylpyrrolidone, etc.

Such nitrogen- and ester-containing polymeric viscosity index improverdispersants are generally employed in concentrations of from about 0.05to 10 wt. % in the fully formulated oil, and preferably from about 0.1to 5 Wt. %, and more preferably from about 0.5 to 3 wt. % can reduce(e.g., to about 0.5 wt. %) the amount of the ashless dispersant employedto provide the required dispersancy to the oil formulation.

Antiwear Agents

Antiwear agents, as their name implies, reduce wear of moving metallicparts. Representative of conventional antiwear agents which may be usedinclude, for example, the zinc dialkyl dithiophosphates, and the zincdiaryl dithiophosphates.

Suitable phosphates include dihydrocarbyl dithiophosphates, wherein thehydrocarbyl groups contain an average of at least 3 carbon atoms.Particularly useful are metal salts of at least one dihydrocarbyldithiophosphoric acid wherein the hydrocarbyl groups contain an averageof at least 3 carbon atoms. The acids from which the dihydrocarbyldithiophosphates can be derived can be illustrated by acids of theformula: ##STR25## wherein R¹⁶ and R¹⁷ are the same or different and arealkyl, cycloalkyl, aralkyl, alkaryl or substituted substantiallyhydrocarbon radical derivatives of any of the above groups, and whereinthe R¹⁶ and R¹¹ groups in the acid each have, on average, at least 3carbon atoms.

By "substantially hydrocarbon" is meant radicals containing substituentgroups (e.g., 1 to 4 substituent groups per radical moiety) such asether, ester, nitro or halogen which do not materially affect thehydrocarbon character of the radical.

Specific examples of suitable R¹⁶ and R¹⁷ radicals include isopropyl,isobutyl, n-butyl, sec-butyl, n-hexyl, heptyl, 2-ethylhexyl, diisobutyl,isooctyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, butylphenyl,o, p-depentylphenyl, octylphenyl, polyisobutene-(molecular weight350)-substituted phenyl, tetrapropylene-substituted phenyl,beta-octylbutylnaphthyl, cyclopentyl, cyclohexyl, phenyl, chlorophenyl,o-dichlorophenyl, bromophenyl, naphthenyl, 2-methylcyclohexyl, benzyl,chlorobenzyl, chloropentyl, dichlorophenyl, nitrophenyl, dichlorodecyland xenyl radicals. Alkyl radicals having about 3 to 30 carbon atoms,and aryl radicals having about 6 to 30 carbon atoms, are preferred.Particularly preferred R¹⁶ and R¹¹ radicals are alkyl of 4 to 18carbons.

The phosphorodithioic acids are readily obtainable by the reaction ofphosphorus pentasulfide and an alcohol or phenol. The reaction involvesmixing, at a temperature of about 20° C. to 200° C., 4 moles of thealcohol or phenol with one mole of phosphorus pentasulfide. Hydrogensulfide is liberated as the reaction takes place. Mixtures of alcohols,phenols or both can be employed, e.g., mixtures of C₃ to C₃₀ alkanols,C₆ to C₃₀ aromatic alcohols, etc.

The metals useful to make the phosphate salts include Group I metals,Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt andnickel. Zinc is the preferred metal. Examples of metal compounds whichmay be reacted with the acid include lithium oxide, lithium hydroxide,lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide,sodium carbonate, sodium methylate, sodium propylate, sodium phenoxide,potassium oxide, potassium hydroxide, potassium carbonate, potassiummethylate, silver oxide, silver carbonate, magnesium oxide, magnesiumhydroxide, magnesium carbonate, magnesium ethylate, magnesium propylate,magnesium phenoxide, calcium oxide, calcium hydroxide, calciumcarbonate, calcium methylate, calcium propylate, calcium pentylate, zincoxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide,strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmiumcarbonate, cadmium ethylate, barium oxide, barium hydroxide, bariumhydrate, barium carbonate, barium ethylate, barium pentylate, aluminumoxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate,tin oxide, tin butylate, cobalt oxide, cobalt hydroxide, cobaltcarbonate, cobalt pentylate, nickel oxide, nickel hydroxide and nickelcarbonate.

In some instances, the incorporation of certain ingredients,particularly carboxylic acids or metal carboxylates such as smallamounts of the metal acetate or acetic acid used in conjunction with themetal reactant will facilitate the reaction and result in an improvedproduct. For example, the use of up to about 5% of zinc acetate incombination with the required amount of zinc oxide facilitates theformation of a zinc phosphorodithioate.

The preparation of metal phosphorodithioates is well known in the artand is described in a large number of issued patents, including U.S.Pat. Nos. 3,293,181; 3,397,145; 3,396,109 and 3,442,804, the disclosuresof which are hereby incorporated by reference insofar as the preparationof metal salts of organic phosphorodithioic acids useful in thisinvention are described.

Also useful as antiwear additives are amine derivatives ofdithiophosphoric acid compounds, such as are described in U.S. Pat. No.3,637,499, the disclosure of which is hereby incorporated by referencein its entirety.

The zinc salts are most commonly used as antiwear additives inlubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %,based upon the total weight of the lubricating oil composition. They maybe prepared in accordance with known techniques by first forming adithiophosphoric acid, usually by reaction of an alcohol or a phenolwith P₂ S₅ and then neutralizing the dithiophosphoric acid with asuitable zinc compound.

Mixtures of alcohols may be used including mixtures of primary andsecondary alcohols, secondary generally for imparting improved antiwearproperties, and primary for thermal stability. Mixtures of the two areparticularly useful. In general, any basic or neutral zinc compoundcould be used but the oxides, hydroxides and carbonates are mostgenerally employed. Commercial additives frequently contain an excess ofzinc due to use of an excess of the basic zinc compound in theneutralization reaction.

The zinc dihydrocarbyl dithiophosphates are oil soluble salts ofdihydrocarbyl esters of dithiophosphoric acids and may be represented bythe following formula: ##STR26## wherein R¹⁶ and R¹⁷ are as described inconnection with the previous formula.

Suitable antiwear agents also comprise the phosphorous- andsulfur-containing product mixtures described in U.S. application Ser.No. 210,831 filed on June 24, 1988 by Ryer and Gutierrez and theContinuation-in-Part thereof: U.S. Ser. No. 370,315, filed Jun. 22,1989, the disclosures thereof are incorporated herein by reference.

In a preferred embodiment of the phosphorous- and sulfur-containingproduct mixtures disclosed in said commonly assigned applications, thefollowing three components, namely: (1) organic phosphite ester, (2)hydrocarbyl thioalkanol, and (3) heterodialkanol are reacted inadmixture, preferably in simultaneous admixture.

Preferred hydrocarbyl thioalkanol reactants include C₈ to C₁₈thioethanols. The preferred heterodialkanols are thiodialkanols.Representative thiodialkanols include 2,2'-thiodiethanol;3,3'-thiodipropanol; thio-bis ethoxy-ethanol;thiobisisopropoxyisopropanol; and mixtures thereof.

Oxidation Inhibitors

Oxidation inhibitors reduce the tendency of mineral oils to deterioratein service, which deterioration can be evidenced by the products ofoxidation such as sludge and varnish-like deposits on the metal surfacesand by viscosity growth.

Useful antioxidant materials include oil soluble phenolic compounds, oilsoluble sulfurized organic compounds, oil soluble amine antioxidants,oil soluble organo borates, oil soluble organo phosphites, oil solubleorganophosphates, oil soluble organo dithiophosphates and mixturesthereof. Preferably such antioxidants are metal-free (that is, free ofmetals which are capable of generating sulfated ash), and therefore aremost preferably ashless (having a sulfated ash value of not greater than1 wt. % SASH, as determined by ASTMD874).

Illustrative of oil soluble phenolic compounds are alkylatedmonophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers,alkylidenebis phenols, benzyl compounds, acylaminophenols, and estersand amides of hindered phenol-substituted alkanoic acids.

Examples of Phenolic Antioxidants

1. Alkylated monophenols 2,6-di-tert-butyl-4-methylphenol;2,6-di-tert-butylphenol; 2-tert-butyl-4,6 dimethylphenol;2,6-di-tertbutyl-4-ethylphenol; 2,6-ditert-butyl-4-ethylphenol;2,6-di-tert-butyl-4-n-butyl-phenol; 2,6-di-tertbutyl-4-isobutylphenol;2,6-dicyclopentyl-4-methylphenol;2-(alpha-methylcyclohexyl)-4,6-dimethylphenol;2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol;2,6-di-tert-butyl-4-methoxymethylphenol; o-tert-butylphenol.

2. Alkylated hydroquinones 2,6-di-tert-butyl-4-methoxyphenol;2,5-di-tertbutyl-hydroquinone; 2,5-di-tert-amylhydroquinone;2,6-di-phenyl-4-octadecyloxyphenol.

3. Hydroxylated thiodiphenyl ethers2,2'-thiobis(6-tert-butyl-4-methyl-phenol); 2,2'-thiobis(4-octylphenol);4,4'-thiobis(6-tert-butyl-3-methylphenol);4,4'-thiobis(6-tert-butyl-2-methylphenol).

4. Alkylidenebisphenols 2,2'-methylenebis(6-tert-butyl-4-methylphenol);2,2'-methylenebis(6-tert-butyl-4-ethylphenol);2,2'-methylenebis[4-methyl-6-(alpha-methylcyclohexyl)-phenol);2,2'-methylenebis(4-methyl-6-cyclohexylphenol);2,2'-methylenebis(6-nonyl-4-methylphenol);2,2'-methylenebis(4,6-di-tert-butyl-phenol);2,2'-methylidenebis(4,6-di-tert-butylphenol);2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol);2,2'-methylenebis[6-alpha-methylbenzyl)-4-nonylphenol];2,2'-methylenebis[6-(alpha, alpha-dimethylbenzyl)-4-nonylphenol];4,4'-methylenebis(2,6-di-tert-butylphenol);4,4'-methylenebis(6-tert-butyl-2-methylphenol);1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;2,6-di(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol;1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane;ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxylphenyl)butyrate];di(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene;di[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tertbutyl-4-methylphenyl]terephthalate.

5. Benzyl compounds1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene;di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide;3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester;bis(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithio-terephthalate;1,3,5-tris(3,5-di-tertbutyl-4-hydroxy-benzyl)isocyanuratel,3,5-tris(4-tertbutyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate;3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid mono-ethyl estercalcium salt.

6. Acylaminophenols 4-hydroxylauric acid anilide; 4-hydroxystearic acidanilide;2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyaniline)-s-triazine;N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.

7. Esters of beta-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol; octadecanol;1,6-hexanediol; neopentyl glycol; thiodiethylene glycol; diethyleneglycol; triethylene glycol; pentaerythritol;tris(hydroxy-ethyl)isocyanurate; and di(hydroxyethyl)oxalic aciddiamide.

8. Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol; octadecanol;1,6-hexanediol; neopentyl glycol; thiodiethylene glycol; diethyleneglycol; triethylene glycol; pentaerythritol; tris(hydroxyethyl)isocyanurate; and di(hydroxyethyl)oxalic acid diamide.

9. Amides of beta -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,e.g.,N,N'-di(3,5-di-tert-butyl-4-hydroxyphenyl-pro-prionyl)hexamethylenediamine;N,N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine;N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

Oil soluble sulfurized organic compounds include those represented bythe formula:

    R.sup.18 S.sub.x.sbsb.4 R.sup.19

wherein S represents sulfur, x₄ is a whole number having a value of from1 to about 10, and R¹⁸ and R¹⁹ may be the same or different organicgroups. The organic groups may be hydrocarbon groups or substitutedhydrocarbon groups containing alkyl, aryl, aralkyl, alkaryl, alkanoate,thiazole, imidazole, phosphorothionate, beta-ketoalkyl groups, etc. Thesubstantially hydrocarbon groups may contain other substituents such ashalogen, amino, hydroxyl, mercapto, alkoxy, aryloxy, thio, nitro,sulfonic acid, carboxylic acid, carboxylic acid ester, etc.

Specific examples of types of sulfurized compositions which are useful.Oxidation inhibitors include aromatic, alkyl or alkenyl sulfides andpolysulfides, sulfurized olefins, sulfurized carboxylic acid esters,sulfurized ester olefins, sulfurized oil, and mixtures thereof. Thepreparation of such oil-soluble sulfurized compositions is described inthe art, and U.S. Pat. No. 4,612,129 is incorporated herein by referencein its entirety for its disclosure of such preparations; including thetype and amount of reactants and catalysts (or promoters), temperaturesand other process conditions, and product purification and recoverytechniques (e.g., decoloring, filtering, and other solids and impurityremoval steps). The sulfurized organic compounds may be aromatic andalkyl sulfides such as dibenzyl sulfide, dixylyl sulfide,dicetylsulfide, diparaffin wax sulfide and polysulfide, cracked waxoleum sulfides, etc.

Examples of dialkenyl sulfides are described in U.S. Pat. No. 2,446,072.Examples of sulfides of this type include6,6'-dithiobis(5-methyl-4-nonene), 2-butenyl monosulfide and disulfide,and 2-methyl-2-butenyl monosulfide and disulfide.

Representative sulfurized olefins include sulfurized olefins prepared bythe reaction of an olefin (preferably containing 3 to 6 carbon atoms) ora lower molecular weight polyolefin derived therefrom, with asulfur-containing compound such as sulfur, sulfur monochloride and/orsulfur dichloride, hydrogen sulfide, etc. Isobutene, propylene and theirdimers, trimers and tetramers, and mixtures thereof are especiallypreferred olefinic compounds. Of these compounds, isobutylene anddiisobutylene are particularly desirable because of their availabilityand the particularly high sulfur-containing compositions which can beprepared therefrom.

The sulfurized organic compounds may be sulfurized oils which may beprepared by treating natural or synthetic oils including mineral oils,lard oil, carboxylic acid esters derived from aliphatic alcohols andfatty acids or aliphatic carboxylic acids (e.g., myristyl oleate andoleyl oleate) sperm whale oil and synthetic sperm whale oil substitutesand synthetic unsaturated esters or glycerides.

The sulfurized fatty acid esters can be prepared by reacting sulfur,sulfur monochloride, and/or sulfur dichloride with an unsaturated fattyester at elevated temperatures. Typical esters include C₁ to C₂₀ alkylesters of C₈ to C₂₄ unsaturated fatty acids such as palmitoleic, oleic,ricinoleic, petroselic, vaccenic, linoleic, linolenic, oleostearic,licanic, etc. Sulfurized fatty acid esters prepared from mixedunsaturated fatty acid esters such as are obtained from animal fats andvegetable oils such as tall oil, linseed oil, olive oil, castor oil,peanut oil, rape oil, fish oil, sperm oil, etc. also are useful.Specific examples of the fatty esters which can be sulfurized includelauryl talate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate,cetyl linoleate, lauryl ricinoleate, oleolinoleate, oleostearate, andalkyl glycerides.

Another class of organic sulfur-containing compounds includes sulfurizedaliphatic esters of an olefinic monodicarboxylic acid. For example,aliphatic alcohols of from 1 to 30 carbon atoms can be used to esterifymonocarboxylic acids such as acrylic acid, methacrylic acid,2,4-pentadienic acid, etc. or fumaric acid, maleic acid, muconic acid,etc. Sulfurization of these esters is conducted with elemental sulfur,sulfur monochloride and/or sulfur dichloride.

Another class of sulfurized organic compounds include diester sulfides.Typical diesters include the butyl, amyl, hexyl, heptyl, octyl, nonyl,decyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl,lauryl, andeicosyl; diesters of thiodialkanoic acids such as propionic,butanoic, pentanoic and hexanoic acids. Of the diester sulfides, aspecific example is dilauryl,3,3'-thiodipropionate.

Other suitable sulfurized organic compound antioxidants include thosederived from a particular type of cyclic or bicyclic olefin which is aDieis-Alder adduct of at least one dienophile with at least onealiphatic conjugated diene. The sulfurized Dieis-Alder adducts can beprepared by reacting various sulfurizing agents with the Dieis-Alderadducts as described more fully below. Typically, the sulfurizing agentis sulfur.

The Diels-Alder adducts are a well-known, art-recognized class ofcompounds prepared by the diene synthesis of Dieis-Alder reaction. Asummary of the prior art relating to this class of compounds is found inthe Russian monograph, "Dienovyi Sintes", Izdatelstwo Akademii NaukSSSR, 1963 by A. S. Onischenko. (Translated into the English language byL. Mandel as A. S. Onischenko, "Diene Synthesis", N.Y., Daniel Davey andCo., Inc., 1964). This monograph and references cited therein areincorporated by reference into the present specification.

Still further sulfurized organic compounds include at least onesulfurized terpene compound or a composition prepared by sulfurizing amixture comprising at least one terpene and at least one other olefiniccompound.

The term "terpene compound" as used in the specification and claims isintended to include the various isomeric terpene hydrocarbons having theempirical formula C₁₀ H₁₆, such as contained in turpentine, pine oil anddipentenes, and the various synthetic and naturally occurringoxygen-containing derivatives. Mixtures of these various compoundsgenerally will be utilized, especially when natural products such aspine oil and turpentine are used. Pine oil, for example, which isobtained by destructive distillation of waste pinewood with super-heatedsteam comprises a mixture of terpene derivatives such asalpha-terpineol, beta-terpineol, alpha-fenchol, camphor,borneol/isoborneol, fenchone, estragole, dihydro alpha-terpineol,anethole, and other monoterpene hydrocarbons. The specific ratios andamounts of the various components in a given pine oil will depend uponthe particular source and the degree of purification. A group of pineoil-derived products are available commercially from HerculesIncorporated. The pine oil products generally known as terpene alcoholsavailable from Hercules Incorporated are particularly useful in thepreparation of this class of sulfurized products. Examples of suchproducts include alpha-Terpineol containing about 95 to 97% ofalpha-terpineol, a high purity tertiary terpene alcohol mixturetypically containing 96.3% of tertiary alcohols; Terpineol 318 Primewhich is a mixture of isomeric terpineols obtained by dehydration ofterpene hydrate and contains about 60 to 65 wt. % of alpha-terpineol and15 to 20% beta-terpineol, and 18 to 20% of other tertiary terpenealcohols. Other mixtures and grades of useful pine oil products also areavailable from Hercules under such designations as Yarmor 302, Hercopine oil, Yarmor 302W, Yarmor F and Yarmor 60.

The above terpene compounds may be sulfurized terpene compounds,sulfurized mixtures of terpene compounds or mixtures of at least oneterpene compound and at least one sulfurized terpene compound.Sulfurized terpene compounds can be prepared by sulfurizing terpenecompounds with sulfur, sulfur halides, or mixtures of sulfur dioxidewith hydrogen sulfide. Also, the sulfurization of various terpenecompounds has been described in the prior art. For example, thesulfurization of pine oil is described in U.S. Pat. No. 2,012,446.

The other olefinic compound which may be combined with the terpenecompound and sulfurized may be any of several olefinic compounds such asthose described earlier.

The other olefin used in combination with the terpene also may be anunsaturated fatty acid, an unsaturated fatty acid ester, mixturesthereof, or mixtures thereof with the olefins described above. The term"fatty acid" as used herein refers to acids which may be obtained byhydrolysis of naturally occurring vegetable or animal fats or oils.These fatty acids usually contain from 16 to 20 carbon atoms and aremixtures of saturated and unsaturated fatty acids. The unsaturated fattyacids generally contained in the naturally occurring vegetable or animalfats and oils may contain one or more double bonds and such acidsinclude palmitoleic acid, oleic acid, linoleic acid, linolenic acid, anderucic acid. The unsaturated fatty acids may comprise mixtures of acidssuch as those obtained from naturally occurring animal and vegetableoils such as lard oil, tall oil, peanut oil, soybean oil, cottonseedoil, sunflower seed oil, or wheat germ oil. Tall oil is a mixture ofrosin acids, mainly abietic acid, and unsaturated fatty acids, mainlyoleic and linoleic acids. Tall oil is a by-product of the sulfateprocess for the manufacture of wood pulp.

The most particularly preferred unsaturated fatty acid esters are thefatty oils, that is, naturally occurring esters of glycerol with thefatty acids described above, and synthetic esters of similar structure.Examples of naturally occurring fats and oils containing unsaturationinclude animal fats such as Neat's foot oil, lard oil, depot fat, beeftallow, etc. Examples of naturally occurring vegetable oils includecottonseed oil, corn oil, poppyseed oil, safflower oil, sesame oil,soybean oil, sunflower seed oil and wheat germ oil.

The fatty acid esters which are useful also may be prepared fromaliphatic olefinic acids of the type described above such as oleic acid,linoleic acid, linolenic acid, and behenic acid by reaction withalcohols and polyols. Examples of aliphatic alcohols which may bereacted with the above-identified acids include monohydric alcohols suchas methanol, ethanol, n-propanol, isopropanol, the butanols, etc.; andpolyhydric alcohols including ethylene glycol, propylene glycol,trimethylene glycol, neopentyl glycol, glycerol, etc.

The sulfurized derivatives of the other olefin compounds can be preparedby methods known in the art utilizing sulfurizing reagents such assulfur, sulfur halides or mixtures of sulfur or sulfur dioxide withhydrogen sulfide.

Exemplary of amine antioxidants are phenyl-substituted andphenylene-substituted amines, N-nitro phenylhydroxylamine, isoindolinecompounds, phosphinodithioic acid-vinyl carboxylate adducts,phosphorodithioate ester-aldehyde reaction products,phosphorodithioate-alkylene oxide reaction products, silyl esters ofterephthalic acid, bis-1,3-alkylamino-2-propanol, anthranilamidecompounds, anthranilic acid esters, alpha-methyl styrenated aromaticamines, aromatic amines and substituted benzophenones, aminoguanidines,peroxide-treated phenothiazine, N-substituted phenothiazines andtriazines, 3-tertiary alkyl-substituted phenothiazines, alkylateddiphenyl-amines, 4-alkylphenyl-1-alkyl-2-naphthylamines, di-benzazepinecompounds, fluorinated aromatic amines, alkylated polyhydroxy benzenoidcompounds, substituted indans, dimethyl octadecylphosphonate-aryliminodi-alkanol copolymers and substituted benzo-diazoborole.

Examples of Amine Antioxidants

N,N,-diisopropyl-p-phenylenediamine;N,N'-di-sec-butyl-p-phenylenediamine;N,N,-bis(1,4-dimethylpentyl)-p-phenylenediamine;N,N,-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine;N,N,-bis(1-methylheptyl)-p-phenyl-enediamine;N,N,-diphenyl-p-phenylenediamine;N,N'-di-(naphthyl-2)-p-phenylenediamine;N-isopropyl-N'-phenyl-p-phenylenediamine;N-(1,3-dimethylbutyl)-N'-phenyl-n-phenylenediamine;N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine;N-cyclohexyl-N'-phenyl-p-phenyl-enediamine;4-(p-toluenesulfonamido)diphenylamine;N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine diphenyl-amine;4-isopropoxydiphenylamine; N-phenyl-1-naphthylamine;N-phenyl-2-naphthylamine; octylated-diphenylamine; 4-n-butylaminophenol;4-butyryl-aminophenol; 4-nonanoylaminophenol; 4-dodecanoyl-aminophenol;4-octadecanoylaminophenol; di-(4-methoxy-phenyl)amine;di-tert-butyl-4-dimethylaminomethylPhenol; 2,4'-diaminodiphenylmethane;4,4'-diaminophenylmethane;N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane;1,2-di[(2-methylphenyl)amino]ethane; 1,2-di(phenylamino)-propane;(o-tolyl)biguanide; di[4-(1',3'-dimethyl-butyl)phenyl]amine;tert-octylated N-phenyl-1-napthyl-amino; and mixture of mono- anddialkylated tert-butyl-tert-octyldiphenylamines.

Oil soluble organo-borate, phosphate and phosphite antioxidants includealkyl- and aryl- (and mixed alkyl, aryl) substituted borates, alkyl- andaryl- (and mixed alkyl, aryl) substituted phosphates, alkyl- and aryl-(and mixed alkyl, aryl) substituted phosphites, and alkyl- and aryl-(and mixed alkyl, aryl) substituted dithiophosphates such asO,O,S-trialkyl dithiophosphates, O,O,S-triaryldithiophosphates anddithiophosphates having mixed substitution by alkyl andaryl groups,phosphorothionyl sulfide, phosphorus-containing silane, polyphenylenesulfide, amine salts of phosphinic acid and quinone phosphates.

A preferred class of antioxidants includes the sulfurizedalkyl-substituted hydroxyaromatic compounds. Sulfurizedalkyl-substituted hydroxyaromatic compounds and the methods of preparingthem are known in the art and are disclosed, for example, in thefollowing U.S. Patents (which are incorporated by reference herein):U.S. Pat. Nos. 2,139,766; 2,198,828; 2,230,542; 2,836,565; 3,285,854;3,538,166; 3,844,956; 3,951,830 and 4,115,287.

In general, the sulfurized alkyl-substituted hydroxyaromatic compoundsmay be prepared by reacting an alkyl-substituted hydroxyaromaticcompound with a sulfurizing agent such as elemental sulfur, a sulfurhalide (e.g., sulfurmonochloride or sulfur dichloride), a mixture ofhydrogen sulfide and sulfur dioxide, or the like. The preferredsulfurizing agents are sulfur and the sulfur halides, and especially thesulfur chlorides, with sulfur dichloride (SC12)being especiallypreferred.

The alkyl-substituted hydroxyaromatic compounds which are sulfurized toproduce antioxidant are generally compounds containing at least onehydroxy group (e.g., from 1 to 3 hydroxy groups) and at least one alkylradical (e.g., from 1 to 3 alkyl radicals) attached to the same aromaticring. The alkyl radical ordinarily contains about 3 to 100, andpreferably about 6 to 20, carbon atoms. The alkyl-substituted hydroxyaromatic compound may contain more than one hydroxy group as exemplifiedby alkyl resorcinols, hydroquinones and catechols, or it may containmore than one alkyl radical; but normally it contains only one of each.Compounds in which the alkyl and hydroxy groups are ortho, meta and parato each other, and mixtures of such compounds, are within the scope ofthe invention. Illustrative alkyl-substituted hydroxyaromatic compoundsare n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol,hexylphenol, heptylphenol, octylphenol, nonylphenol, n-dodecylphenol,(propenetetramer)-substituted phenol, octadecylphenol, eicosylphenol,polybutene (molecular weight about 1000)-substituted phenol,n-dodecylresorcinol and 2,4-di-t-butylphenol, and the alkyl-substitutedcatechols corresponding to the foregoing. Also included aremethylene-bridged alkyl-substituted hydroxyaromatic compounds of thetype which may be prepared by the reaction of an alkyl-substitutedhydroxyaromatic compound with formaldehyde or a formaldehyde-yieldingreagent such as trioxane or paraformaldehyde.

The sulfurized alkyl-substituted hydroxy-aromatic compound is typicallyprepared by reacting the alkyl-substituted hydroxyaromatic compound withthe sulfurizing agent at a temperature within the range of about 100° C.to 250° C. The reaction may take place in a substantially inert diluentsuch as toluene, xylene, petroleum naphtha, mineral oil, Cellosolve orthe like. If the sulfurizing agent is a sulfur halide, and especially ifno diluent is used, it is frequently preferred to remove acidicmaterials such as hydrogen halides by vacuum stripping the reactionmixture or blowing it with an inert gas such as nitrogen. If thesulfurizing agent is sulfur, it is frequently advantageous to blow thesulfurized product with an inert gas such as nitrogen or air so as toremove sulfur oxides and the like.

Also useful herein are antioxidants disclosed in the following U.S.Patents, the disclosures of which are herein incorporated by referencein their entirety: U.S. Pat. Nos. 3,451,166; 3,458,495; 3,470,099;3,511,780; 3,687,848; 3,770,854; 3,850,822; 3,876,733; 3,929,654;4,115,287; 4,136,041; 4,153,562; 4,367,152 and 4,737,301.

The most preferred antioxidants include oil soluble copper compounds.The copper may be blended into the oil as any suitable oil solublecopper compound. By oil soluble we mean the compound is oil solubleunder normal blending conditions in the oil or additive package. Thecopper compound may be in the cuprous or cupric form. The copper may bein the form of the copper dihydrocarbyl thio- or dithiophosphateswherein copper may be substituted for zinc in the compounds andreactions described above although 1 mole of cuprous or cupric oxide maybe reacted with 1 or 2 moles of the dithiophosphoric acid, respectively.Alternatively, the copper may be added as the copper salt of a syntheticor natural carboxylic acid. Examples include C₁₀ to C₁₈ fatty acids suchas stearic or palmitic, but unsaturated acids such as oleic or branchedcarboxylic acids such as napthenic acids of molecular weight from 200 to500 or synthetic carboxylic acids are preferred because of the improvedhandling and solubility properties of the resulting copper carboxylates.Also useful are oil soluble copper dithiocarbamates of the generalformula (RR'NCSS)_(n) Cu, where n is 1 or 2 and R and R' are the same ordifferent hydrocarbyl radicals containing from 1 to 18 and preferably 2to 12 carbon atoms and including radicals such as alkyl, alkenyl, aryl,aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred asR and R' groups are alkyl groups of 2 to 8 carbon atoms. Thus, theradicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl,i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl,dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl,methylcyclopentyl, propenyl, butenyl, etc. In order to obtain oilsolubility, the total number of carbon atoms (i.e., R and R') willgenerally be about 5 or greater. Copper sulphonates, phenates, andacetylacetonates may also be used.

Exemplary of useful copper compound antioxidants are copper (Cu^(I)and/or Cu^(II)) salts of alkenyl carboxylic acids or anhydrides such assuccinic acids or anhydrides. The salts themselves may be basic, neutralor acidic. They may be formed by reacting (a) any of the functionalizedpolymers which are useful as dispersants section, which have at leastone free carboxylic acid (or anhydride) group with (b) a reactive metalcompound. Suitable acid (or anhydride) reactive metal compounds includethose such as cupric or cuprous hydroxides, oxides, acetates, borates,and carbonates or basic copper carbonate.

Examples of the metal salts are Cu salts of poly-n-butene succinicanhydride (hereinafter referred to as Cu--PNBSA) polyisobutenyl succinicanhydride (hereinafter referred to as Cu--PIBSA), and Cu salts ofpoly-n-butene or polyisobutenyl succinic acid. Preferably, the selectedmetal employed is its divalent form, e.g., Cu+². The preferredsubstrates are polyalkenyl carboxylic acids in which the alkenyl grouphas a molecular weight greater than about 700. The alkenyl groupdesirably has a Mn from about 900 to 1,500, and up to 5,000. Thesematerials can be dissolved in a solvent, such as a mineral oil, andheated in the presence of a water solution (or slurry) of the metalbearing material. Heating may take place between 70° C. and about 200°C. Temperatures of 110° C. to 140° C. are entirely adequate. It may benecessary, depending upon the salt produced, not to allow the reactionto remain at a temperature above about 140° C. for an extended period oftime, e.g., longer than 5 hours, or decomposition of the salt may occur.

The copper antioxidants (e.g., Cu--PIBSA, Cu--PNB, Cu--oleate, ormixtures thereof) will be generally employed in an amount of from about50 to 500 ppm by weight of the metal, in the final lubricating or fuelcomposition.

The copper antioxidants are inexpensive and are effective at lowconcentrations and therefore do not add substantially to the cost of theproduct. The results obtained are frequently better than those obtainedwith previously used antioxidants, which are expensive and used inhigher concentrations. In the amounts employed, the copper compounds donot interfere with the performance of other components of thelubricating composition, in many instances, completely satisfactoryresults are obtained when the copper compound is the sole antioxidant inaddition to the ZDDP. The copper compounds can be utilized to replacepart or all of the need for supplementary antioxidants. Thus, forparticularly severe conditions it may be desirable to include asupplementary, conventional antioxidant. However, the amounts ofsupplementary antioxidant required are small, far less than the amountrequired in the absence of the copper compound.

While any effective amount of the copper antioxidant can be incorporatedinto the lubricating oil composition, it is contemplated that sucheffective amounts be sufficient to provide said lube oil compositionwith an amount of the copper antioxidant of from about 5 to 500 (morepreferably 10 to 200, still more preferably 10 to 180, and mostpreferably 20 to 130 (e.g., 90 to 120)) ppm of added copper based on theweight of the lubricating oil composition. Of course, the preferredamount may depend, amongst other factors, on the quality of thebasestock lubricating oil.

Corrosion Inhibitors

Corrosion inhibitors, also known as anti-corrosive agents, reduce thedegradation of the metallic parts contacted by the lubricating oilcomposition. Illustrative of corrosion inhibitors are phosphosulfurizedhydrocarbons and the products obtained by reaction of aphosphosulfurized hydrocarbon with an alkaline earth metal oxide orhydroxide, preferably in the presence of an alkylated phenol or of analkylphenol thioester, and also preferably in the presence of carbondioxide. Phosphosulfurized hydrocarbons are prepared by reacting asuitable hydrocarbon such as a terpene, a heavy petroleum fraction of aC₂ to C₆ olefin polymer such as polyisobutylene, with from 5 to 30 wt. %of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in therange of 65° C. to 315° C. Neutralization of the phosphosulfurizedhydrocarbon may be effected in the manner taught in U.S. Pat. No.2,969,324.

Other suitable corrosion inhibitors include copper corrosion inhibitorscomprising hydrocarbyl-thio-distributed derivatives of1,3,4-thiadiazole, e.g., C₂ to C₃₀ ; alkyl, aryl, cycloalkyl, aralkyland alkaryl-mono-, di-, tri-, tetra- or thio-substituted derivativesthereof.

Representative examples of such materials included2,5-bis(octylthio)-1,3,4-thiadiazole;2,5-bis(octyl-dithio)-1,3,4-thiadiazole;2,5-bis(octyltrithio)-1,3,4-thiadiazole;2,5-bis(octyltetrithio)-1,3,4-thiadiazole;2,5-bis(nonylthio)-1,3,4-thiadiazole;2,5-bis(dodecyl-dithio)-1,3,4-thiadiazole;2-dodecyldithio-5-phenyl-dithio-1,3,4-thiadiazole; 2,5-bis(cyclohexyldithio)-1,3,4-thiadiazole; and mixtures thereof.

Preferred copper corrosion inhibitors are the derivative of-1,3,4-thiadiazoles such as those described in U.S. Pat. Nos. 2,719,125,2,719,126 and 3,087,932; especially preferred is the compound2,5-bis(t-octyldithio)-1,3,4-thiadiazole commercially available as Amoco150, and 2,5-bis(t-nonyldithio)-1,3,4-thiadiazole, commerciallyavailable as Amoco 158.

The preparation of such materials is further described in U.S. Pat. Nos.2,719,125, 2,719,126, 3,087,932 and 4,410,436, the disclosures of whichare hereby incorporated by reference.

Corrosion inhibitors also include copper lead bearing corrosioninhibitors. Typically such compounds are the thiadiazole polysulphidescontaining from 5 to 50 carbon atoms, their derivatives and polymersthereof. Preferred materials are the derivatives of 1,3,4-thiadiazolessuch as those described in U.S. Pat. Nos. 2,719,125; 2,719,126 and3,087,932; especially preferred is the compound 2,5bis(t-octadithio)-1,3,4-thiadiazole, commercially available as Amoco150. Other similar materials also suitable are described in U.S. Pat.Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299and 4,193,882.

Other suitable corrosion inhibitors are the thio and polythiosulphenamides of thiadiazoles such as those described in U.K. PatentSpecification 1,560,830. These compounds can be included in thelubricating composition in an amount from 0.01 to 10, preferably 0.1 to5.0 wt. % based on the weight of the composition.

Friction Modifiers

Friction modifiers serve to impart the proper friction characteristicsto lubricating oil compositions such as automatic transmission fluids.Representative examples of suitable friction modifiers are found in U.S.Pat. No. 3,933,659 which discloses fatty acid esters and amides; U.S.Pat. No. 4,176,074 which describes molybdenum complexes ofpolyisobutenyl succinic anhydride-amino alkanols; U.S. Pat. No.4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S.Pat. No. 3,779,928 which discloses alkane phosphonic acid salts; U.S.Pat. No. 3,778,375 which discloses reaction products of a phosphonatewith an oleamide; U.S. Pat. No. 3,852,205 which disclosesS-carboxy-alkylene hydrocarbyl succinimide, S-carboxy alkylenehydrocarbyl succinamic acid and mixtures thereof; U.S. Pat. No.3,879,306 which discloses N-(hydroxyalkyl) alkenyl-succinamic acids orsuccinimides; U.S. Pat. No. 3,932,290 which discloses reaction productsof di-(lower alkyl) phosphites and epoxides; and U.S. Pat. No. 4,028,258which discloses the alkylene oxide adduct of phosphosulfurizedN-(hydroxyalkyl) alkenyl succinimides. The disclosures of the abovereferences are herein incorporated by reference. Preferred frictionmodifiers are include hydroxy amines, as disclosed in U.S. Pat. No.5,078,893 and the thioether hydroxyamines as disclosed in U.S.S.N.211,428 filed June 24, 1988; glycerol mono and dioleates; succinateesters, or metal salts thereof, of hydrocarbyl substituted succinicacids or anhydrides and thiobis alkanols such as described in U.S. Pat.No. 4,344,853 and amide friction modifiers such as the reaction productof isostearic acid and tetraethylene pentamine as disclosed in commonlyassigned U.S. Ser. No. 425,939, filed October 24, 1989 (our filePTF-048), all of which are herein incorporated by reference.

Anti-Foamants

Foam control can be provided by an antifoamant of the polysiloxane type,e.g. silicone oil and polydimethyl siloxane.

Rust Inhibitors

Organic, oil-soluble compounds useful as rust inhibitors comprisenonionic surfactants such as polyoxyalkylene polyols and esters thereof,and anionic surfactants such as salts of alkyl sulfonic acids. Suchanti-rust compounds are known and can be made by conventional means.Nonionic surfactants, useful as anti-rust additives in oleaginouscompositions usually owe their surfactant properties to a number of weakstabilizing groups such as ether linkages. Nonionic anti-rust agentscontaining ether linkages can be made by alkoxylating organic substratescontaining active hydrogens with an excess of the lower alkylene oxides(such as ethylene and propylene oxides) until the desired number ofalkoxy groups have been placed in the molecule.

The preferred rust inhibitors are polyoxyalkylene polyols andderivatives thereof. This class of materials are commercially availablefrom various sources: Pluronic Polyols from Wyandotte ChemicalsCorporation; Polyglycol 112-2, a liquid triol derived from ethyleneoxide and propylene oxide available from Dow Chemical Co.; and Tergitol,dodecylphenyl or monophenyl polyethylene glycol ethers, and Ucon,polyalkylene glycols and derivatives, both available from Union CarbideCorp. These are but a few of the commercial products suitable as rustinhibitors.

In addition to the polyols per se, the esters thereof obtained byreacting the polyols with various carboxylic acids are also suitable.Acids useful in preparing these esters are lauric acid, stearic acid,succinic acid, and alkyl- or alkenyl-substituted succinic acids whereinthe alkyl or alkenyl group contains up to about 20 carbon atoms.

The preferred polyols are prepared as block polymers. Thus, ahydroxy-substituted compound, R-(OH)n (wherein n is 1 to 6, and R is theresidue of a mono- or polyhydric alcohol, phenol, naphthol, etc.) isreacted with propylene oxide to form a hydrophobic base. This base isthen reacted with ethylene oxide to provide a hydrophylic portionresulting in a molecule having both hydrophobic and hydrophylicportions. The relative sizes of these portions can be adjusted byregulating the ratio of reactants, time of reaction, etc., as is obviousto those skilled in the art. Typically, the ethylene oxide units willcomprise from about 10 to about 40%, preferably from about 10 to about15% by weight of the moleucle. Number average molecular weight of thepolyol is from about 2,500 to 4,500. The polyols having a moleculeweight of about 4,000 with about 10% attributable to ethylene oxideunits are particularly good.

Thus it is within the skill of the art to prepare polyols whosemolecules are characterized by hydrophobic and hydrophylic moietieswhich are present in a ratio rendering rust inhibitors suitable for usein any lubricant composition regardless of differences in the base oilsand the presence of other additives.

If more oil-solubility is needed in a given lubricating composition, thehydrophobic portion can be increased and/or the hydrophylic portiondecreased. If greater oil-in-water emulsion breaking ability isrequired, the hydrophylic and/or hydrophobic portions can be adjusted toaccomplish this.

Compounds illustrative of R--(OH)n include alkylene polyols such as thealkylene glycols, alkylene triols, alkylene tetrols, etc., such asethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol,mannitol, and the like. Aromatic hydroxy compounds such as alkylatedmono- and polyhydric phenols and naphthols can also be used, e.g.,heptylphenol, dodecylphenol, etc.

Also useful rust inhibitors are alkoxylated fatty amines, amides,alcohols and the like, including such alkoxylated fatty acid derivativestreated with C₉ to C₁₆ alkyl-substituted phenols (such as the mono- anddi-heptyl, octyl, nonyl, decyl, undecyl, dodecyl and tridecyl phenols),as described in U.S. Pat. No. 3,849,501, which is also herebyincorporated by reference in its entirety.

Demulsifiers

Suitable demulsifiers include the esters disclosed in U.S. Pat. Nos.3,098,827 and 2,674,619 herein incorporated by reference.

Lube Oil Flow Improvers

Lubricating oil flow improvers (LOFI) include all those additives whichmodify the size, number, and growth of wax crystals in lube oils orfuels in such a way as to impart improved low temperature handling,pumpability, and/or vehicle operability as measured by such tests aspour point and mini rotary viscometry (MRV). The majority of flowimprovers are polymers or contain polymers. These polymers are generallyof two types, either backbone or sidechain.

The backbone variety, such as the ethylene-vinyl acetates (EVA), havevarious lengths of methylene segments randomly distributed in thebackbone of the polymer, which associate or cocrystallize with the waxcrystals inhibiting further crystal growth due to branches andnon-crystallizable segments in the polymer.

The sidechain type polymers, which are the predominant variety used asLOFI's, have methylene segments as the sidechains, preferably asstraight side-chains. The polymers work similarly to the backbone typeexcept the sidechains have been found more effective in treatingisoparaffins as well as n-paraffins found in lube oils. Representativeof this type of polymer are C₈ to C₁₈ dialkylfumarate/vinyl acetatecopolymers, polyacrylates, polymethacrylates, and esterifiedstyrene-maleic anhydride copolymers.

Seal Swell Agents

Seal swellants include mineral oils of the type that provoke swelling ofengine seals, including aliphatic alcohols of 8 to 13 carbon atoms suchas tridecyl alcohol, with a preferred seal swellant being characterizedas an oil-soluble, saturated, aliphatic or aromatic hydrocarbon ester offrom 10 to 60 carbon atoms and 2 to 4 linkages, e.g., dihexyl phthalate,as are described in U.S. Pat. No. 3,974,081.

Some of the above numerous additives can provide a multiplicity ofeffects e.g., a dispersant oxidation inhibitor. This approach is wellknown and need not be further elaborated herein.

Compositions, when containing these additives, typically are blendedinto the base oil in amounts which are effective to provide their normalattendant function. Representative effective amounts of such additivesare illustrated as follows:

    ______________________________________                                                         (Broad)  (Preferred)                                         Compositions     Wt %     Wt %                                                ______________________________________                                        V. I. Improver      1-12   1-4                                                Corrosion Inhibitor                                                                            0.01-3   0.01-1.5                                            Oxidation Inhibitor                                                                            0.01-5   0.01-1.5                                            Dispersant        0.1-10  0.1-5                                               Lube Oil Flow Improver                                                                         0.01-2   0.01-1.5                                            Detergents and Rust                                                                            0.01-6   0.01-3                                              Inhibitors                                                                    Pour Point Depressant                                                                            0.01-1.5                                                                             0.01-1.5                                            Anti-Foaming Agents                                                                             0.001-0.1                                                                             0.001-0.01                                          Antiwear Agents  0.001-5  0.001-1.5                                           Seal Swellant     0.1-8   0.1-4                                               Friction Modifiers                                                                             0.01-3   0.01-1.5                                            Lubricating Base Oil                                                                           Balance  Balance                                             ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the subject additives of this invention (inconcentrate amounts hereinabove described), together with one or more ofsaid other additives (said concentrate when constituting an additivemixture being referred to herein as an additive-package) whereby severaladditives can be added simultaneously to the base oil to form thelubricating oil composition. Dissolution of the additive concentrateinto the lubricating oil may be facilitated by solvents and by mixingaccompanied with mild heating, but this is not essential. Theconcentrate or additive-package will typically be formulated to containthe additives in proper amounts to provide the desired concentration inthe final formulation when the additive-package is combined with apredetermined amount of base lubricant. Thus, the subject additives ofthe present invention can be added to small amounts of base oil or othercompatible solvents along with other desirable additives to formadditive-packages containing active ingredients in collective amounts oftypically from about 2.5 to about 90%, and preferably from about 15 toabout 75%, and most preferably from about 25 to about 60% by weightadditives in the appropriate proportions with the remainder being baseoil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

All of said weight percents expressed herein (unless otherwiseindicated) are based on active ingredient (AI) content of the additive,and/or upon the total weight of any additive-package, or formulationwhich will be the sum of the A.I. weight of each additive plus theweight of total oil or diluent.

The invention is further illustrated by the following examples which arenot to be considered as limitative of its scope.

EXAMPLES

The following examples and comparative examples are set forth toillustrate the nature of the invention and the method of carrying itout. However, the invention should not be considered as being limited tothe details thereof. Composition parts and percents are by weight unlessotherwise indicated. All molecular weights (Mn) are number averagemolecular weight.

EXAMPLES 1-13 Yield of Carboxylic Acid Group (Examples 1-5) EXAMPLE 1(Comparative)

34.5 parts of poly-n-butene polymer (PNB) (Mn=550) dissolved in 36.2parts of n-heptane (nC7) were charged to an autoclave, mixed and heatedto 50° C. 662 parts of BF₃ dihydrate (BF₃ ·2H₂ O) were then chargedfollowed immediately by CO which brought the total autoclave pressure to1500 psig. The mixture was stirred for 3 hours at temperature andpressure. Pressure was released, and the reaction product was washedwith copious amounts of water and butanol to free the polymer phase fromthe acid phase. The polymer was dried in an oven. The analysis of thefinished polymer showed less than 5% conversion to the carboxylic acidgroup.

EXAMPLE 2

The procedure described in Example 1 was then followed except, 37.1parts of PNB (Mn=550) was dissolved in 40.2 parts of nC₇, and 690 partsof BF₃ ·1.2H₂ O was substituted for the BF₃ ·2H₂ O. The BF₃ ·2H₂ O wasprepared by bubbling BF₃ gas into BF₃ ·2H₂ O until sufficient BF₃ wasabsorbed to give the desired composition. The pressure was brought to2000 psig with CO. The analysis of the final product showed 85%conversion of the polymer to neo-carboxylic acid.

EXAMPLE 3

The procedure described in Example 1 was followed except that 203.6parts of ethylene propylene (EP) copolymer (Mn=1800, and about 50 wt. %ethylene) and 159.9 parts of nC₇, and 34 parts of BF₃ ·1.1 H₂ O weresubstituted for the charges of reactants. The pressure was brought to2000 psi with CO. The conversion to neo-carboxylic acid was 56%.

EXAMPLE 4

The procedure described in Example 1 was followed except 803 parts ofEthylene Butylene (EB) copolymer (Mn=3700 about 45 wt. % ethylene), 568parts of iso-octane, and 670 parts of BF₃ =1.1 H₂ O were used. Thepressure was brought to 2000 psig with CO. The reaction product wasdischarged into an aqueous solution containing 600 parts of sodiumfluoride (NaF), 756 parts of water, 302 parts of hexane, and 50 parts ofbutanol. The polymer product readily separated from the aqueous phase,was recovered, and dried. The analysis showed 85.1% conversion toneo-carboxylic acid.

EXAMPLE 5

The procedure described in Example 4 was followed except 543 parts ofpropylene butylene (PB) copolymer (Mn=2800, and about 30 wt. %propylene) 454 parts of iso-octane, and 659 parts of BF₃ ·1.1 H₂ O wereused. The reaction product was discharged into 600 parts sodiumfluoride, 945 parts water, and 302 parts hexane. The analysis of thefinal product showed 75.4% conversion to neo-carboxylic acid.

The results of Examples 1-5 are summarized in Table 1 below:

                  TABLE 1                                                         ______________________________________                                                                    Catalyst  Yield                                   Example   Polymer  Mn       Complex   (%)                                     ______________________________________                                        Comp.                                                                         1         PNB       550     BF.sub.3.2H.sub.2 O                                                                     <5                                      2         PNB       550     BF.sub.3.1.2H.sub.2 O                                                                   85                                      3         EP       1800     BF.sub.3.1.1H.sub.2 O                                                                   56                                      4         EB       3700     BF.sub.3.1.1H.sub.2 O                                                                   85.1                                    5         PB       2800     BF.sub.3.1.1H.sub.2 O                                                                   75.4                                    ______________________________________                                    

Yield of Alkylester (Examples 6-13) EXAMPLE 6 (Comparative)

The procedure described in Example 1 was followed except, 1119.2 partsof PNB (Mn=550) without solvent, and 350 parts of BF₃ ·dibutanol(prepared by bubbling BF₃ gas into n-butanol) were used. The pressurewas brought to 2000 psig with CO. The analysis of the final productshowed less than 5% conversion to neo-alkyl ester.

EXAMPLE 7

The procedure described in Example 1 was followed except, 153.3 parts ofEP polymer (Mn=900, about 50 wt. % ethylene) and 137.9 parts nC₇, and 88parts of BF₃ ·monobutanol was used in the recipe. The polymer was dried,and the conversion to neo-alkyl ester was 86%.

EXAMPLE 8

The procedure as described in Example 4 was followed except 143 parts ofPNB (Mn=550), without solvent, and 37 parts of BF₃ ·monomethanol(prepared by bubbling BF₃ gas into methanol) (BF₃ ·CH₃ OH) was used. Thereaction product was discharged into 230 parts of ammonium fluoride and765 parts methanol. The conversion was 91.3% to the neo-methyl ester.

Yield of Aryl Ester EXAMPLE 9

The procedure described in Example 1 was followed except 440 parts ofPNB (Mn=550), without solvent, and 244 parts of BF₃ ·tetra(4-chlorophenol) was used. The BF₃ complex was prepared by bubbling BF₃gas into melted 4-chlorophenol. The autoclave was pressured to 1485 psigwith CO, and the reaction was held at 55° C. for 2 hours. The analysisshowed the following results:

    ______________________________________                                        Yield to 4 chloro phenyl neo-ester/acid                                                            = 60% of polymer                                         to alkyl phenyl ester                                                                              = 11.7% of polymer                                       to alkyl phenol      = 10.1% of polymer                                       Total Yield          = 81.8% polymer                                                                    converted                                           ______________________________________                                    

EXAMPLE 10

A complex of BF₃ with 4-chlorophenol was prepared by bubbling BF₃ intomelted 4-chlorophenol. In order to enhance the uptake of BF₃ gas togenerate BF₃ ·di(4-chlorophenol) the solution was cooled. After severalminutes, the solution solidified. Melting the complex resulted in rapidliberation of BF₃.

EXAMPLE 11

An autoclave was charged with 391 psig of BF₃ gas at 30° C., followed byan additional 118 psig of CO, to a total pressure of about 500 psig.While stirring the autoclave, a mixture of 440 parts PNB (Mn=550) and108 parts of 3-fluoro-phenol was charged to the reactor , and thepressure was brought to 1500 psig with CO, and the temperature to 50° C.The reaction was held at these conditions for 2 hours and the autoclavewas then depressurized. The reaction product was stripped to remove BF₃gas, and excess substituted phenol. The final product analysis showed91.5% yield.

EXAMPLE 12

The procedure of Example 11 was followed, except the autoclave waspressured to 199 psig with BF₃ at 50° C., followed by 301 psig of CO, tobring the total pressure to 500 psig and 406 parts of EB copolymer(Mn=4600, 20 wt. % ethylene) and 100.6 parts of 2,4-dichlorophenol(pKa=7.85) at 50° C. were charged to the autoclave and pressured to 1430psig with CO. The yield was 84.5%.

EXAMPLE 13

The procedure in Example 11 was followed except the autoclave waspressured to 254 psig with BF₃ at 50° C., followed by 254 psig of CO tobring the total pressure to 508 psig; and, 110 parts EB polymer(Mn=2200, about 50% ethylene) 31 parts of dichlorophenol (pKa=7.85) at50° C. were charged to the autoclave, and pressurized to 2000 psig withCO. The conversion was 85.4%.

The results of Examples 6-9 and 11-13 are summarized in Table 2 below:

                  TABLE 2                                                         ______________________________________                                                                Catalyst      Yield                                   Example                                                                              Polymer  Mn      Complex       (%)                                     ______________________________________                                        Comp.                                                                         6      PNB      550     BF.sub.3.dibutanol                                                                          <5                                      7      EP       900     BF.sub.3.monobutanol                                                                        86                                      8      PNB      550     monomethanol  91.3                                    9      PNB      550     BF.sub.3.tetra(4-chloro-                                                                    81.8                                                            phenol                                                11     PNB      550     *BF.sub.3 + 3-fluoro-                                                                       91.5                                                            phenol                                                12     EB       4600    *BF.sub.3 2,4-dichloro-                                                                     84.5                                    13     EB       2200    *BF.sub.3 + dichlorophenol                                                                  85.4                                    ______________________________________                                         *Catalyst and phenolic compound added separately in one step.            

EXAMPLE 14-18 Amination Reaction of PNB-neo carboxylic acid with PAMEXAMPLE 14

200 parts the PNB neocarboxylic acid prepared by a process similar tothat of Example 2 and 31.2 parts of poly(ethyleneamine) averaging 5-8nitrogens per molecule (PAM) were charged into a reactor with stirring.The reactor contents were purged with nitrogen. The reactor was sealedand the pressure was brought to 60 psig with nitrogen. The reactor washeated to 240° C. for five hours. The contents were then sparged withnitrogen via a dip tube and overhead vent line and cooled at 30° C. Theyield of carboxylic acid amide by ¹³ C-NMR was 45.4%.

EXAMPLE 15

374 parts of neo acid functionalized EB copolymer of Example 4 dissolvedin 700 parts heptane were charged to a reactor vessel. The solution washeated with mixing to 90° C. Then, 70 parts of thionyl chloride wasslowly added to the solution, plus an additional 300 parts of heptane.After the reaction to the acid chloride was complete, the solution washeated to 100° C. at atmospheric pressure with N₂ sparging followed byhigh vacuum flashing to remove reaction by products and heptane. Theacid chloride product was cooled. Then, fresh, dry heptane was added tothe acid chloride product. The acid chloride product was then heated to90° C. Then, 10 parts of polyamine (PAM) and 17.8 parts of triethylaminewere slowly added to the acid chloride. The reaction mixture wasfiltered and excess triethylamine was stripped to produce the aminatedproduct as shown by infrared analysis.

EXAMPLE 16

17.8 parts of the 2,4-dichlorophenyl ester of the EB copolymer ofExample 12 were charged to a reaction vessel. The vessel contents wereheated to 80° C. with mixing. Then 0.442 parts of polypmine (PAM) wascharged to the vessel. The vessel contents were than slowly heated overa period of 8 hours from 150° C. to 220° C. while refluxing theliberated dichlorophenol (pKa=7.85). After complete conversion to theamide, the phenol was removed by N₂ sparging. The vessel contents werecooled to ambient temperature. Carbon 13 NMR analysis showedquantitative conversion of ester to amide.

EXAMPLE 17

The procedure as described in Example 16 was followed, except 20.2 partsof the 2,4-dichlorophenyl ester of Example 13 was used with 0.954 partsof PAM. The carbon¹³ NMR analysis showed quantitative conversion ofester to amide.

EXAMPLE 18

19.4 parts of the aminated polymer described in Example 17 was mixedwith 10.0 parts of base oil and heated to 140° C. in a reaction vesselwith mixing. Then 1.407 parts of milled 30% boric acid slurry in baseoil was slowly added to the vessel contents. The reactor was spargedwith N₂ at temperature for two hours, then an additional 6.26 parts ofbase oil was added to the reaction vessel. The vessel contents werecooled to 120° C., and filtered. The analysis of the product showed a45% active ingredient level (0.73% N, 0.26 % B).

What is claimed is:
 1. A composition comprising functionalized polymerof the formula: ##STR27## wherein POLY- is derived from unsaturatedpolymer other than gem-structured polyolefin, the unsaturated polymerhaving a number average molecular weight prior to functionalization ofat least about 500, n is a number greater than 0 and represents thefunctionality of the functionalized polymer, R¹ and R² are the same ordifferent and are selected from the group consisting of hydrogen,hydrocarbyl, and polymeric hydrocarbyl, with the proviso that R¹ and R²are selected such that at least 50 mole percent of the ##STR28## groupshave both R¹ and R² not hydrogen, Y is selected from the groupconsisting of 0 and S, and R³ is selected from H and hydrocarbyl.
 2. Thecomposition of claim 1 wherein in said formula I, Y represents
 0. 3. Thecomposition of claim 1 wherein in said formula Y represents S.
 4. Thecomposition of any one of claims 1 to 3 wherein 1≧n>0.
 5. Thecomposition of any one of claims 1 to 3 wherein 2≧n>1.
 6. Thecomposition of any one of claims 1 to 3 wherein n>2.
 7. The compositionof claim 1 wherein the unsaturated polymer from which POLY- is derivedhas a number average molecular weight of at least about 2,800.
 8. Thecomposition of claim 1 wherein the unsaturated polymer from which POLY-is derived is selected from homopolymers or copolymers formed from thepolymerization of monomers selected from the group consisting of olefin,diolefin, and mixtures.
 9. The composition of claim 7 wherein theunsaturated polymer is selected from the group consisting ofpoly-n-butenes, ethylene-propylene copolymers, ethylene-propylene dienepolymers, styrene butadiene copolymers, and methylstyrene butadienecopolymers.
 10. The composition of any one of claims 1 to 3 wherein theunsaturated polymer from which POLY- is derived is selected from thegroup consisting of ethylene alpha-olefin copolymer, poly (alpha-olefin)homopolymer, and poly (alpha-olefin) copolymer.
 11. A compositioncomprising functionalized polymer of the formula: ##STR29## whereinPOLY- is derived from unsaturated polymer having a number averagemolecular weight prior to functionalization of at least about 500, n isa number greater than 0 and represents the functionality of thefunctionalized polymer, R¹ and R² are the same or different and areselected from the group consisting of H, hydrocarbyl, substitutedhydrocarbyl, and polymeric hydrocarbyl, with the proviso that R¹ and R²are selected such that at least 50 mole percent of the ##STR30## groupshave both R¹ and R² not hydrogen, Y is selected from the groupconsisting of O and S, and R³ is selected from the group consisting ofsubstituted hydrocarbyl, aryl, substituted aryl, and mixtures thereof.12. The composition of claim 11 wherein the group --Y--R³, when existingas free compound HY--R³, has a pKa at room temperature in water of lessthan or equal to
 12. 13. The composition of claim 12 wherein R³ has theformula: ##STR31## wherein each X, which may be the same or different,represents an electron withdrawing group, each T, which may be the sameor different, represents a non-electron withdrawing substituent, and mand p are from 0 to 5 with the sum of m and p being from 0 to
 5. 14. Thecomposition of claim 13 wherein m is at least 1, X is selected from thegroup consisting of halogen, --CF₃, cyano and nitro, and p=0 or
 1. 15.The composition as recited in claim 14 wherein m is
 2. 16. Thecomposition as recited in claim 14 wherein in formula II, n is from 1 to3; X is selected from Cl, F, and CF₃ ; and m is from 2 to
 5. 17. Thecomposition of claim 14 wherein X is halogen, and T can be methyl orhydroxy.
 18. The composition of claim 11 wherein Y is
 0. 19. Thecomposition of claim 11 wherein 1≧n≧0.
 20. The composition of claim 11wherein 2≧n>1.
 21. The composition of claim 11 wherein n>2.
 22. Thecomposition of claim 12 wherein the pKa at room temperature in water ofthe HY--R³ compound is less than or equal to about
 8. 23. Thecomposition of claim 11 wherein the molecular weight distribution of thepolymer from which POLY- is derived is from about 1.5 to about 5.0. 24.The composition of claim 11 wherein R¹ and R² are selected such that atleast 90 mole percent of the parenthetical substituent are neo-acylgroups.
 25. The composition of claim 11 wherein the unsaturated polymerfrom which POLY- is derived is selected from homopolymers or copolymersformed from the polymerization of at least one of monoolefin, diolefinand mixtures.
 26. The composition of claim 11 wherein the unsaturatedpolymer from which POLY- is derived is selected from alpha-olefinhomopolymer, alpha-olefin copolymer, or ethylene-alpha olefin copolymer.27. The composition of claim 26 wherein the unsaturated polymer fromwhich POLY- is derived is formed from the polymerization of monomerselected from the group consisting of ethylene, propylene, n-butenes,isobutylene, pentene, hexene, heptene, octene, nonene, decene, isoprene,hexadiene, and mixtures thereof.
 28. The composition of claim 11 whereinthe unsaturated polymer from which POLY- is derived is selected from thegroup consisting of polypropylene, poly-n-butene, polyisobutene,ethylene-propylene copolymers, ethylene-propylene diene polymers,ethylene-butene copolymers, butene-propylene copolymers,styrene-isobutene copolymers, isobutene-butadiene-1,3 copolymer,propene-isoprene copolymers, isobutene chloroprene copolymer,isobutene-(para-methyl)styrene copolymer, copolymers of hexene-1 withhexadiene-1,3, copolymer of octene-1, copolymer of 3,3dimethyl-pentene-1 with hexene-1, and terpolymer of isobutene, styreneand piperylene.
 29. The composition of claim 11 wherein the polymer fromwhich POLY- is derived has a number average molecular weight of at leastabout 2,000.
 30. The composition of claim 11 wherein the polymer fromwhich POLY- is derived has a number average molecular weight of at leastabout 2,000 and is selected from the group consisting of poly-n-butenes,ethylene-butene copolymer, butylene-propylene copolymer.
 31. Thecomposition of any one of claims 11, and 25 to 30 wherein the polymerfrom which POLY- is derived has a number average molecular weight of upto about 15,000,000.
 32. The composition of claim 31 wherein the polymerhas a number average molecular weight of from about 1000 to about20,000.
 33. The composition of claim 31 wherein the polymer has a numberaverage molecular weight of from about 1500 to about 10,000.
 34. Thecomposition of claim 31 wherein the polymer has a number averagemolecular weight of from about 2,000 to about 8,000.
 35. The compositionof claim 31 wherein the polymer has a number average molecular weight offrom about 20,000 to about 200,000.
 36. The composition of claim 31wherein the polymer has a number average molecular weight of from about25,000 to about 100,000.
 37. The composition of claim 31 wherein thepolymer has a number average molecular weight of from about 25,000 toabout 80,000.
 38. The composition of claim 31 wherein the polymer has anumber average molecular weight of from about 25,000 to about 65,000.39. A derivatized polymer composition comprising the reaction productof:(A) a functionalized polymer of the formula: ##STR32## wherein POLY-is derived from unsaturated polymer other than gem-structuredpolyolefin, the unsaturated polymer having a number average molecularweight prior to functionalization of at least about 500, n is a numbergreater than 0 and represents the functionality of the functionalizedpolymer, R¹ and R² are the same or different and are selected from thegroup consisting of hydrogen, hydrocarbyl, and polymeric hydrocarbyl,with the proviso that R¹ and R² are selected such that at least 50 molepercent of the ##STR33## groups have both R¹ and R² not hydrogen, Y isselected from the group consisting of 0 and S, and R³ is selected from Hand hydrocarbyl; and (B) a derivatizing compound.
 40. The derivatizedcomposition as recited in claim 39 wherein the derivatizing compound isa nucleophilic reactant.
 41. The derivatized composition as recited inclaim 40 wherein the nucleophilic reactant compound is selected from thegroup consisting of amine, alcohol, amino-alcohol, reactant metalcompound, and mixtures thereof.
 42. The derivatized composition asrecited in claim 41 wherein the derivatizing compound is selected fromthe group consisting of polyamine, polyol and mixtures thereof.
 43. Thederivatized composition of claim 39 adapted for use as a dispersantwherein the polymer from which POLY- is derived has dispersant rangemolecular weight.
 44. The derivatized composition of claim 39 adaptedfor use as a multifunctional viscosity index improver wherein thepolymer from which POLY- is derived has multifunctional viscositymodifier range molecular weight.
 45. The composition of any one ofclaims 1 to 3 wherein the molecular weight distribution of the polymerfrom which POLY- is derived is from about 1.5 to about 5.0.
 46. Thecomposition of any one of claims 1 to 3 wherein R¹ and R² are selectedsuch that at least 90 mole percent of the parenthetical substituent areneo-acyl groups.
 47. The composition of any one of claims 1 to 3,wherein the unsaturated polymer from which POLY- is derived is ethylenealpha-olefin polymer comprising ethylene, alpha-olefin and anonconjugated polyene.
 48. The composition of claim 11 wherein theunsaturated polymer from which POLY- is derived is ethylene alpha-olefinpolymer comprising ethylene, alpha-olefin and a nonconjugated polyene.49. A derivatized polymer composition comprising the reaction productof:(A) a functionalized polymer of the formula: ##STR34## wherein POLY-is derived from unsaturated polymer other than gem-structuredpolyolefin, the unsaturated polymer having a number average molecularweight prior to functionalization of at least about 500, n is a numbergreater than 0 and represents the functionality of the functionalizedpolymer, R¹ and R² are the same or different and are selected from thegroup consisting of hydrogen, hydrocarbyl, and polymeric hydrocarbyl,with the proviso that R¹ and R² are selected such that at least 50 molepercent of the ##STR35## groups have both R¹ and R² not hydrogen, Y isselected from the group consisting of 0 and S, and R³ is selected fromthe group consisting of substituted hydrocarbyl, aryl, substituted aryl,and mixtures thereof; and (B) a derivatizing compound.
 50. A lubricatingoil composition comprising base oil and from about 0.1 to about 10 wt. %of the derivatized polymer composition of claim
 39. 51. A lubricatingoil concentrate comprising base oil and from about 10 to about 80 wt. %of the derivatized polymer composition of claim
 39. 52. A lubricatingoil concentrate comprising base oil and from about 5 to about 50 wt. %of the derivatized polymer composition of claim
 39. 53. A fuelcomposition comprising fuel and from about 0.001 to about 0.5 wt. % ofthe derivatized polymer composition of claim
 39. 54. A lubricating oilcomposition comprising base oil and from about 0.1 to about 10 wt. % ofthe derivatized polymer composition of claim
 49. 55. A lubricating oilconcentrate comprising base oil and from about 10 to about 80 wt. % ofthe derivatized polymer composition of claim
 49. 56. A lubricating oilconcentrate comprising base oil and from about 5 to about 50 wt. % ofthe derivatized polymer composition of claim
 49. 57. A fuel compositioncomprising fuel and from about 0.001 to about 0.5 wt. % of thederivatized polymer composition of claim
 49. 58. A compositioncomprising functionalized polymer of the formula: ##STR36## whereinPOLY- is derived from unsaturated polymer having a number averagemolecular weight prior to functionalization of at least about 500; n isa number greater than 0 and represents the functionality of thefunctionalized polymer; and R¹ and R² are the same or different and areselected from the group consisting of hydrogen, hydrocarbyl, andpolymeric hydrocarbyl, with the proviso that R¹ and R² are selected suchthat at least 50 mole percent of the ##STR37## groups have both R¹ andR² not hydrogen.
 59. The derivatized composition as recited in claim 49,wherein the derivatizing compound is a nucleophilic reactant.
 60. Thederivatized composition as recited in claim 59, wherein the nucleophilicreactant compound is selected from the group consisting of amine,alcohol, amino-alcohol, reactant metal compound, and mixtures thereof.61. The derivatized composition as recited in claim 60, wherein thederivatizing compound is selected from the group consisting ofpolyamine, polyol and mixtures thereof.
 62. The derivatized compositionof claim 49 adapted for use as a dispersant wherein the polymer fromwhich POLY- is derived has dispersant range molecular weight.
 63. Thederivatized composition of claim 49 adapted for use as a multifunctionalviscosity index improver wherein the polymer from which POLY- is derivedhas multifunctional viscosity modifier range molecular weight.